Patent Application
20130316938
The present invention relates to a particular class of compounds capable of releasing fragrant compounds in a controlled manner into the surroundings. The present invention is also concerned with a process for their production, and consumer products comprising them.
The provision of fragrance in products by addition thereto of inherently fragrant substances to products is well known and widely used. An alternative method of providing fragrance is by the use of a precursor, that is, a substance that is itself, basically because of the high molecular weight, essentially odorless, but which, in particular circumstances, will decompose to release the fragrant molecule.
There are several classes of compounds known which release fragrant molecules upon activation, such as hydrolysis, temperature change, oxygen, action of light and enzymes. According to our best knowledge only two classes of compounds have been reported to release upon oxidative cleavage odoriferous compounds. JP 2001-072637 discloses 2-alkoxy-3-arylpropenals (A) releasing functional substances. There are no details given with regard to the release mechanism nor with regard to any functional substance thus released. Yang et al. (Helv. Chim. Acta 2003, 86, 2928-2936) reports the release of aldehydes and ketones of p-amino alcohols (B) by periodate oxidation in H2O (=water).
The systems reported in the prior art are often either too stable or too unstable and are therefore rather unsuitable as delivery systems for the controlled release of fragrances. It is therefore necessary to reach an optimal balance between stability and instability so as to obtain a release rate of the precursors as required for different applications, a task which is very difficult to achieve. In addition, the p-amino alcohols (B) described by Yang et al. release the aldehyde/ketone only in the presence of periodate, an additive which is not accepted in consumer products.
It has now been found that the compounds of formula (I) as hereinbelow described can act as precursors for the release, by spontaneous air oxidation, of an aldehyde or ketone and a further fragrant compound containing a carbonyl group.
Thus, there is provided in one aspect the use of a compound of formula (I)
as precursor for generating a ketone or aldehyde of the formula (II)
and a carbonyl compound of the formula (III)
wherein
R1 is selected from the group consisting of C5-C14 alkyl, for example C6-C12 such as C8, C9, C10 or C11 alkyl;
C5-C14 alkenyl, for example C6-C12 such as C8, C9, C10 or C11 alkenyl comprising, e.g. one or two carbon-to-carbon double bonds;
C5-C6 cycloalkyl such as cyclohexyl, or cyclopentyl;
C5-C8 cycloalkyl (e.g. cyclohexyl, cyclopentyl) substituted with 1, 2, or 3 groups selected from C1-C6 alkyl (e.g. ethyl, isopropyl, tert-pentyl) and C2-C4 alkylidene (e.g. isopropenyl);
C5-C8 cycloalkenyl, e.g. C6 cycloalkenyl such as cyclohexa-2,4-dienyl, cyclohex-1-enyl, cyclooct-3-enyl;
C5-C8 cycloalkenyl such as cyclooct-3-enyl, wherein the cycloalkenyl-ring is substituted with 1, 2, or 3 groups selected from C1-C4 alkyl (e.g. ethyl, or isopropyl), C2-C4 alkylidene (e.g. isopropenyl), and C3-C5 cycloalkyl (e.g. R1 is 7-methyl-spiro[4.5]dec-8-en-6-yl, spiro[4.5]dec-7-en-7-yl, 5,5-dimethylcyclohex-1-enyl, 2,6,6-trimethylcyclohex-1,3-dienyl, 2,4-dimethylcyclohex-3-enyl, or 4-isopropenyl(cyclohex-1en-1yl);
(C1-C3)alkyl(C5-C6)cycloalkyl wherein the cycloalkyl-ring is optionally substituted with one group selected from —OH group and ═O group, and/or one or two ether group(s), and/or up to four C1-C5 alkyl groups (e.g. R1 is (3-tertbutylcyclohexyl)ethyl, or (4-(1,1-dimethylpropyl)cyclohexyl)methyl, (3-oxo-2-pentylcyclopentyl)methyl);
(C1-C4)alkyl(C5-C6)cycloalkenyl wherein the cycloalkenyl-ring is optionally substituted with one —OH group, and/or one or two ether group(s), and/or up to four (i.e. 0, 1, 2, 3 or 4) C1-C5 alkyl groups (e.g. (2,6,6-trimethylcyclohex-1-en-1-yl)ethyl, 1-(2,6,6-trimethylcyclohex-2-en-1-yl)butan-3-yl);
(C2-C3)alkenyl(C5-C6)cycloalkenyl wherein the cycloalkenyl-ring is optionally substituted with one —OH group, and/or one or two ether group(s), and/or up to four (i.e. 0, 1, 2, 3, or 4) C1-C5 alkyl groups (e.g. (2,6,6-trimethylcyclohex-1-en-1-yl)ethenyl, (2,6,6-trimethylcyclohex-2-en-1-yl)ethenyl, (2,6,6-trimethylcyclohex-2-en-1-yl)prop-2-en-2-yl, (2,6,6-trimethylcyclohex-1-en-1-yl)prop-2-en-2-yl);
C6-C14 aryl, e.g. phenyl;
C6-C14 aryl wherein the aryl ring is substituted with up to 3 (i.e. 0, 1, 2, or 3) groups selected from C1-C4 alkyl (e.g. ethyl, iso-propyl, tert-butyl), —O—CH2—O—, and —OR11 wherein R11 is independently selected from hydrogen and C1-C4 alkyl (e.g. ethyl, iso-propyl, tert-butyl);
(C1-C3)alkyl(C6-C14)aryl, e.g. benzyl, 2-phenylethyl;
(C1-C3)alkyl(C6-C14)aryl such as benzyl or 2-phenylethyl wherein the aryl-ring is substituted with up to 2 groups (e.g. 1 group) selected from C1-C4 alkyl (e.g. ethyl, iso-propyl, tert-butyl), —O—CH2—O—, and —OR12 wherein R12 is independently selected from hydrogen and C1-C4 alkyl (e.g. ethyl, iso-propyl, tert-butyl);
(C2-C8)alkenyl(C6-C14)aryl, e.g. 2-phenylethylene-1-yl, 1-phenylhept-1-en-2-yl; (C2-C8)alkenyl(C6-C14)aryl wherein the aryl-ring is substituted with up to 2 groups (e.g. 1 group) selected from C1-C4 alkyl (e.g. ethyl, iso-propyl, tert-butyl), —O—CH2—O—, and —OR13 wherein R13 is independently selected from hydrogen and C1-C4 alkyl (e.g. ethyl, iso-propyl, tert-butyl); bi-, tri, or tetracyclic hydrocarbon ring comprising C8-C12 carbon atoms optionally substituted with up to 6 groups selected from C1-C4 alkyl (e.g. ethyl, iso-propyl, tert-butyl), —O—CH2—O—, and —OR14 wherein R14 is independently selected from hydrogen and C1-C4 alkyl (e.g. ethyl, iso-propyl, tert-butyl), e.g. R1 is 1,1,6,7-tetramethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-7-yl, 2-((1,1-dimethyl-(2,3-dihydro-1H-indene))-6-yl)-eth-1-yl, 3,6,8,8-tetramethyl-2,3,4,7,8,8a-hexahydro-1H-3a,7-methanoazulen-5(4H)-ylidene, or 1,1,2,4,4,7-hexamethyl-1,2,3,4-tetrahydronaphthalene-6-yl;
R2 is selected from hydrogen, C1-C5 alkyl, and C2-C5 alkenyl (e.g. but-3-enyl);
or
R1 and R2 form together with the carbon atom to which they are attached
R3 is hydrogen or methyl; and
X means a radical of formula (Ia)
with the proviso that
a) if n=0, R1 is not a group selected from aryl and aryl substituted with an —OR11 wherein R11 is C1-C4 alkyl; and
b) if R3 is hydrogen and R1 is selected from the group consisting of alkenyl, alkenylcycloalkenyl, alkenylaryl and cycloalkenyl in which no sp3-hybridised C-atom is between C-1′ and the nearest C—C double bond of R1, then n=1.
Non-limiting examples are compounds of formula (I) wherein X is phenyl optionally substituted with up to 3 (i.e. 0, 1, 2 or 3) groups selected from C1-C4 alkyl (e.g. methyl, ethyl, iso-propyl, tert-butyl), vinyl, hydroxy, C1-C3 alkoxy (e.g. ethoxy), and —O—CH2—O—, e.g. X is benzo[d][1,3]dioxol-5-yl, 3-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 4-vinylphenyl or 3-ethoxy-4-hydroxyphenyl.
Further, non-limiting examples are compounds of formula (I) wherein X is a radical of formula (Ia)
wherein R5 is hydrogen or methyl and R6 and R7 form together with the C-3 and C-4 a 5 or 6 membered ring (e.g. cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1,3-dioxolane) wherein the ring may optionally substituted with up to 5 methyl groups (e.g. 1 or 2 methyl groups).
Further, non-limiting examples are compounds of formula (I) wherein X is a radical of formula (Ib)
wherein n=0 or 1, R4 and R5 independently of each other are selected from hydrogen and methyl, and R6 and R7 independently of each other are selected from hydrogen, C1-C5 alkyl, vinyl, hydroxyl, methoxy or ethoxy.
Further, non-limiting examples are compounds of formula (I) wherein X is selected from naphthyl (e.g. naphth-2-yl), (naphthyl)methyl, 1,1,2,4,4,7-hexamethyl-1,2,3,4-tetrahydronaphthalen-6-yl, and 1,1,2,4,4,-pentamethyl-1,2,3,4-tetrahydronaphthalen-7-yl.
Further non-limiting examples are compounds of formula (I) wherein R1 is C1, C2 or C3 alkylphenyl wherein the phenyl ring is substituted with up to 3 (i.e. 0, 1, 2 or 3) groups selected from C1-C4 alkyl (e.g. iso-propyl, tert-butyl), hydroxy, C1-C3 alkoxy (e.g. ethoxy), and
—O—CH2—O—.
Further, non-limiting examples are compounds of formula (I) wherein R2 is hydrogen and R3 is hydrogen or methyl.
Further, non-limiting examples are compounds of formula (I) wherein R2 is hydrogen or methyl and R3 is hydrogen.
Further, non-limiting examples are compounds of formula (I) wherein n=0, R2 and R3 are independently selected from hydrogen and methyl, R6 is selected from hydrogen, methyl and hydroxyl, and R7 is selected form hydrogen, methoxy and ethoxy, with the proviso that if R6 is hydroxyl than R7 is methoxy or ethoxy.
Further, non-limiting examples are compounds of formula (I) wherein R2 is hydrogen or methyl, R3 is hydrogen, and R1 is (C1-C3)alkyl(C6-C14)aryl wherein the aryl-ring is optionally substituted with one group selected from methoxy and hydroxyl.
Further, non-limiting examples are compounds of formula (I) wherein R1 is C5-C14 alkenyl comprising one carbon-to-carbon double bond, R2 is hydrogen, and R3 is hydrogen, with the proviso that the carbon-to-carbon double bond is not in alpha position to C-1′.
Further, non-limiting examples are compounds of formula (I) wherein R1 is C5-C14 alkenyl comprising one carbon-to-carbon double bond, R2 is hydrogen, and R3 is methyl.
As used in relation to compounds of formula (I) unless otherwise indicated “alkyl” refers to linear or branched alkyl wherein the alkyl residue may comprise up to one —OH group and up to 2 (i.e. 0, 1 or 2) ether group(s), such as undecan-2-yl, 2,4,4-trimethylpentyl, 2,6-dimethylheptyl, and 6-methylheptan-2-yloxypropyl; “alkenyl” refers to linear or branched alkyl comprising at least one carbon-to-carbon double bond, e.g. 2 or 3 double bonds, the alkenyl may optionally comprise a —OH group and/or ether group, for example oct-1,5-dienyl, non-3-enyl, and 2,6-dimethylhept-1,5-dienyl; “hydrocarbon ring” refers to saturated and unsaturated ring systems, preferably containing up to two carbon-to-carbon double bonds per ring, wherein the ring may be substituted with up to 3 (e.g. one or two) C1-C3 alkyl; and “ether group” refers to an oxygen atom connected to two carbon atoms.
With regard to the compounds of formula (I) the wavy bond means that the arrangement at the ethylenic double bond may be either in E- or Z-configuration.
All the compounds of formula (I) hereinabove described have in common the fact that, on exposure to ambient air they release volatile compounds over a long period of time (e.g. several days such as 2-7 days or even longer). In a preferred embodiment, at least one of the released compounds is a fragrant compound. In a further embodiment the compound of formula (II) is a fragrant aldehyde (for R2═H) or ketone (for R2≠H) and a second compound is a fragrant carbonyl compound of formula (III).
Examples of fragrant aldehydes O═CHR1 which may be released from the compound of formula (I) under activating conditions include, but are not limited to, the following: benzaldehyde, 2,6,10-trimethylundec-9-enal, 8,8-dimethyl-1,2,3,4,5,6,7,8-octahydro-naphthalene-2-carbaldehyde, (4-isopropyl-phenyl)-ethanal, 2,4-dimethyl-cyclohex-3-ene-1-carbaldehyde, 1,3,5-trimethyl-cyclohex-1-ene-4-carbaldehyde, 4-(4-hydroxy-4-methylpentyl)-cyclohex-3-ene-1-carbaldehyde, hex-2-enal, hex-3-enal (including (Z)-hex-3-enal), 3-(3-tert-butylcyclohexyl)propanal, 2-(4-tert-pentylcyclohexyl)acetaldehyde, 3,5,5-trimethyl-hexanal, heptanal, 2,6-dimethyl-hept-5-enal, decanal, dec-9-enal, dec-4-en-1-al, 2-methyl-decanal, undec-10-en-1-al, undecanal, dodecanal, 2-methyl-undecanal, tridecanal, tridec-2-enal, octanal, nonanal, non-2-enal, undec-9-enal, 2-phenyl-propanal, 2-(4-methyl-phenyl)-ethanal, 2-(4-methoxyphenyl)acetaldehyde, 3,7-dimethyl-octanal, dihydrofarnesal (3,7,11-trimethyldodeca-6,10-dienal), 7-hydroxy-3,7-dimethyl-octanal, 2,6-dimethyl-oct-5-en-1-al, 3-(3-isopropyl-phenyl)-butanal (Florhydral), 4-(4-methyl-pent-3-enyl)-cyclohex-3-ene-1-carbaldehyde, 2,3,5,5,-tetramethyl-hexanal, decahydro-4,8,8-trimethyl-1,4-methanoazulene-9-carboxaldehyde (longifolic aldehyde), 2-methyl-3-(4-tert-butylphenyl)-propanal (Lilial), 3-(4-tert-butyl-phenyl)-propanal, 3-(4-isobutyl-phenyl)-propanal, 3-(benzo[1,3]dioxol-5-yl)-2-methyl-propanal, 3,7-dimethyl-oct-6-ene-1-al, 3,7-dimethyl-octanal, 2-methyl-3-(4-isopropylphenyl)-propanal, 4-tert-butyl-cyclohexane-1-carbaldehyde, 4-(octahydro-4,7-methano-5H-inden-5-ylidene)-butanal, (3,7-dimethyl-oct-6-enyloxy)-ethanal, 2 (E),6 (Z)-nonadienal, 2,4-dimethyl-2,6-heptadienal, (E)-dec-2-enal, dodec-2-enal, 3,7-dimethyl-octa-2,6-dienal, 2,4-diethyl-hepta-2,6-dienal, 3,7-dimethyl-nona-2,6-dienal, 2-propyl-hept-2-enal, 3-(4-methoxyphenyl)-2-methylpropanal, 4-methoxybenzaldehyde, 1,3-benzodioxole-5-carboxaldehyde, 2,6,6-trimethylcyclohexa-1,3-dienecarbaldehyde, 4-((6-methylheptan-2-yl)oxy)butanal, 3-(4-ethylphenyl)-2,2-dimethylpropanal, (E)-2-benzylideneheptanal, cinnamaldehyde, 3-(3,3-dimethyl-2,3-dihydro-1H-inden-5-yl)propanal, 2-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)butanal (Cetonal) and 4-isopropenyl-cyclohex-1-ene-1-carbaldehyde.
Examples of fragrant ketones O═CR1R2 which may be released from the compound of formula (I) under activating conditions include, but are not limited to, the following: Raspberry Ketone (4-(4-hydroxyphenyl)butan-2-one), lonones such as alpha-lonone, dihydro alpha-lonone, dihydro beta-lonone, N-allyl alpha-ionone (1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-1,6-heptadien-3-one), beta-lonone, N-methyl alpha-ionone (1-(2,6,6-trimethylcyclohex-2-en-1-yl)pent-1-en-3-one), dimethyl alpha-ionone (2-methyl-1-(2,6,6-trimethylcyclohex-2-en-1-yl)pent-1-en-3-one), and Cetone Alpha (3-methyl-4-(2,6,6-trimethylcyclohex-2-en-1-yl)but-3-en-2-one), Nectaryl (2-(2-(4-methylcyclohex-3-en-1-yl)propyl)cyclopentanone), Magnolione (3-(2-oxopropyl)-2-pentylcyclopentanone), Acetophenone, Oranger Crist (1-(naphthalen-2-yl)ethanone) and Cassione (4-(benzo[d][1,3]dioxol-5-yl)butan-2-one).
Examples of fragrant compounds of formula (III) O═CR3X which may be released from the compound of formula (I) under activating conditions include, but are not limited to, the following: Ethylvanilin, Vanillin, Oranger Crist (1-(naphthalen-2-yl)ethanone), acetophenone, Heliotropine (1,3-benzodioxole-5-carboxaldehyde), anisic aldehyde, veratric aldehyde, phenylacetic aldehyde, Syringa Aldehyde (4-methyl phenylacetaldehyde), benzaldehyde, 3-methyl-benzaldehyde, 1-(4-methoxyphenyl)ethanone (Acetanisole), 4-(1-methylethyl)-benzenacetaldehyde, Ambral (2,4-(di-(1,1-dimethylethyl))-5-methoxy-benzaldehyde), 4-isopropyl-benzaldehyde, 1-(2,4-dimethylphenyl)ethanone, Fixal (5,5,7,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalene-2-carbaldehyde), Fixolide (1-(3,5,5,6,8,8-hexamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)ethanone), Florantone T (1-(5,6,7,8-tetrahydronaphthalen-2-yl)ethanone), 1-(1,1,2,3,3,6-hexamethyl-2,3-dihydro-1H-inden-5-yl)ethanone, 2-(4-isopropylphenyl)propanal, Vulcanolide (3,5,5,6,7,8,8-heptamethyl-5,6,7,8-tetrahydronaphthalene-2-carbaldehyde) and Safraleine (2,3,3-trimethyl-2,3-dihydro-1H-inden-1-one).
The activating conditions, which lead to the cleavage step, comprise the presence of molecular oxygen. The concentration of oxygen in the air is sufficient for cleaving the compound of formula (I) in such a way, that the cleavage products can be detected in the ambient air, e.g. by olfaction or GC-MS analysis of headspace samples.
The compounds of formula (I) are very stable when not exposed to the ambient air, i.e. when stored in a diluent conventionally used in conjunction with odorants, such as dipropyleneglycol (DPG), isopropylmyristate (IPM), triethylcitrate (TEC) and alcohol (e.g. ethanol), and known odorants. Very good storage stability has been proven also when incorporated in consumer products such as detergent, shampoo and fabric conditioner. 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 compounds of formula (I) can act as fragrance precursors in functional and fine perfumery i.e. in fine fragrances, industrial, institutional, home and personal care products. Industrial, institutional and home cleaning 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 conditioner compositions. A substrate, such as a fabric, treated with a product comprising a compound of formula (I), will diffuse a fresh and/or clean odor under cleavage conditions for much longer than one treated with a conventional product. Fabrics or clothes washed with such a fabric softener will exhibit noticeable fragrance release even after one week.
The compounds of the formula (I) are also useful for application in all kinds of body care products. Especially interesting products are hair care products, for example shampoos, conditioners and hairsprays, and skin care products.
The abovementioned examples are of course only illustrative and non-limiting. Many other products to which the compounds of formula (I) may be added include soaps, bath and shower gels and deodorants.
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 fragrance ingredients are 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.
The amounts in which the compounds of formula (I) may be incorporated in the various above-mentioned products vary within a wide range. The amounts depend on the nature of the fragrant compounds to be released, the nature of the product to which the compounds of formula (I) are added and the desired olfactory effect. The amounts used also depend on the co-ingredients in a given composition when the compounds of formula (I) are used in admixture with perfuming co-ingredients, solvents or adjuvants. Typical concentrations are from 0.0001 to 5 weight percent of the article. In one embodiment, compounds of the present invention may be employed in a fabric softener in an amount of from 0.0001 to 0.2 weight percent. In another embodiment, compounds of the present invention may be used in fine perfumery in amounts from 0.001 to 10 weight percent (e.g. up to about 5 weight percent), more preferably between 0.02 and 4 weight percent. 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.
While some of the compounds falling within the definition of the formula (I) above are known as intermediates, others are novel.
The invention therefore also provides a compound of formula (I) as hereinabove defined selected from (3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)pent-2-enyl)benzene; (5,9-dimethyldec-2-enyl)benzene; (4-methyltridec-2-enyl)benzene; (3-(2,4-dimethylcyclohex-3-enyl)allyl)benzene; (4-methyldodec-2-enyl)benzene; 1-isopropyl-3-(6-phenylhex-4-en-2-yl)benzene; but-2-ene-1,3-diyldibenzene; ((4E)-3-methyl-5-(2,6,6-trimethylcyclohex-1-enyl)penta-2,4-dienyl)benzene; (3-methyldodec-2-enyl)benzene; 5-(3-methyl-5-phenylpent-3-enyl)benzo[d][1,3]dioxole; ((4E)-3,4-dimethyl-5-(2,6,6-trimethylcyclohex-2-enyl)penta-2,4-dienyl)benzene; (4E,8Z)-undeca-2,4,8-trienylbenzene; (6E)-dodeca-2,6-dienylbenzene; 1-tert-butyl-4-(2-methyl-5-phenylpent-3-enyl)benzene; 1-(2,2-dimethyl-5-phenylpent-3-enyl)-4-ethylbenzene; (5,7,7-trimethyloct-2-enyl)benzene; (6-(6-methylheptan-2-yloxy)hex-2-enyl)benzene; (5-(3-tert-utylcyclohexyl)pent-2-enyl)benzene; (4-(4-tert-pentylcyclohexyl)but-2-enyl)benzene; 2-ethoxy-4-(3-phenylprop-1-enyl)phenol; 4-(3-methyl-5-phenylpent-3-enyl)phenol; 2-ethoxy-4-(3-p-tolylprop-1-enyl)phenol; 2-ethoxy-4-(3-(4-methoxyphenyl)prop-1-enyl)phenol; 1-methoxy-4-(4-methyltridec-2-enyl)benzene; 1-isopropyl-3-(6-(4-methoxyphenyl)hex-4-en-2-yl)benzene; 1-((6E)-dodeca-2,6-dienyl)-4-methoxybenzene; 2-(4-(4-methoxyphenyl)but-2-en-2-yl)naphthalene; 1-tert-butyl-4-(5-(4-methoxyphenyl)-2-methylpent-3-enyl)benzene; 1-methyl-4-(4-methyltridec-2-enyl)benzene; 1-((6E)-dodeca-2,6-dienyl)-4-methylbenzene; 1-tert-butyl-4-(2-methyl-5-p-tolylpent-3-enyl)benzene; 1-methyl-4-((4E)-3-methyl-5-(2,6,6-trimethylcyclohex-1-en-1-yl)penta-2,4-dien-1-yl)benzene; 5-(3-p-tolylprop-1-enyl)benzo[d][1,3]dioxole; 2-(4-methyltridec-2-enyl)naphthalene; 4-(3-methyl-4-phenylbut-3-enyl)phenol; 2-ethoxy-4-(4-(4-hydroxyphenyl)-2-methylbut-1-enyl)phenol; 2-ethoxy-4-(4-(3-isopropylphenyl)pent-1-enyl)phenol; 2-ethoxy-4-(3-methyldodec-1-enyl)phenol; 2-ethoxy-4-((2-(2-(4-methylcyclohex-3-enyl)propyl)cyclopentylidene)methyl)-phenol; 2-(5-(3-isopropylphenyl)hex-2-en-2-yl)naphthalene; 2-((4E,8Z)-undeca-2,4,8-trien-2-yl)naphthalene; 2-((6E)-dodeca-2,6-dien-2-yl)naphthalene; 2-(4-methyltridec-2-en-2-yl)naphthalene; 2-(5,7,7-trimethyloct-2-en-2-yl)naphthalene; 4-(4-(3-isopropylphenyl)pent-1-enyl)-1,2-dimethoxybenzene; 1,2-dimethoxy-4-(4-(4-methoxyphenyl)-3-methylbut-1-enyl)benzene; 5-(4-(3-isopropylphenyl)pent-1-enyl)benzo[d][1,3]dioxole; 5-(4-(4-methoxyphenyl)-3-methylbut-1-enyl)benzo[d][1,3]dioxole; 5-(4-(4-tert-butylphenyl)-3-methylbut-1-enyl)benzo[d][1,3]dioxole; 1-methoxy-4-(3-(p-tolyl)prop-1-en-1-yl)benzene; 1-(tert-butyl)-4-(4-(4-methoxyphenyl)-2-methylbut-3-en-1-yl)benzene; 4-(4-(4-methoxyphenyl)-3-methylbut-3-en-1-yl)phenol; 1-isopropyl-3-(5-(4-methoxyphenyl)pent-4-en-2-yl)benzene; 1-isobutyl-4-(4-(4-methoxyphenyl)but-3-en-1-yl)benzene; 2-((11E)-trideca-2,11-dien-2-yl)naphthalene; 5-(4-phenylbut-1-en-1-yl)benzo[d][1,3]dioxole; 1,2-dimethoxy-4-(3-(4-(prop-1-en-2-yl)cyclohex-1-en-1-yl)allyl)benzene; 2-(5-(4-(tert-butyl)phenyl)-4-methylpent-2-en-2-yl)naphthalene; 2-((4E)-5,9-dimethyldeca-2,4,8-trien-2-yl)naphthalene; 2-(5-phenylpent-2-en-2-yl)naphthalene; 2-((4E)-tetradeca-2,4-dien-2-yl)naphthalene; 3-(3-(4-methoxyphenyl)-2-methylallyl)-2-pentylcyclopentanone; 1-methoxy-4-[(5E)-undeca-1,5-dien-1-yl]benzene; 1-methoxy-4-(3-methyldodec-1-en-1-yl)benzene; (1E)-1-[(4Z)-hepta-1,4-dien-1-yl]-4-methoxybenzene; (1Z)-1-[(4Z)-hepta-1,4-dien-1-yl]-4-methoxybenzene; and 4-[3-methyl-4-(m-tolyl)but-3-en-1-yl]phenol.
The compounds of formula (I) may be prepared starting from the respective fragrant carbonyl compound of formula (II) as hereinabove defined and a phosphorous ylide derived in situ from a 1- or 2-arylethyltriphenyl-phosphonium-halogen salt or an aryltriphenyl-phosphonium-halogen salt.
The phosphonium salts may be synthesized from the corresponding alkyl halides and triphenlyphosphine. The reaction can be carried out without solvent in a sealed tube or a round bottom flask at a temperature preferably between about 130-150° C. Alternatively, the reaction may be conducted in a round bottom flask in a solvent e.g. toluene, THF or MeCN and at a temperature between about 25-140° C. Benzylic phosphonium salts may also be synthesized from the corresponding benzylalcohols and triphenylphoshine hydrobromide. The reaction is conducted in a solvent e.g. toluene, THF or MeCN and at a temperature between about 25-140° C. The phosphorous ylides may be prepared from the crude phosphonium salts through deprotonation with a suitable base, e.g. R′Li, NaH, NaOR″ or KOR″, with R′ being e.g. methyl, butyl or t-butyl and R″ being e.g. methyl, ethyl, t-amyl or t-butyl. The reaction may be carried out in a solvent, e.g. THF or toluene. The base is added to the phosphonium salt at a temperature between about minus 78° C. to about 25° C.
The desired fragrant ketone/aldehyde of formula (II) may be added to the in situ prepared phosphorous ylide, preferably at a temperature between about minus 78° C. to about 25° C. and the reaction mixture may be stirred at a temperature between about 0-70° C.
Alternatively, the compounds of formula (I) may be prepared starting from the respective aldehyde/ketone of formula (III) as hereinabove defined and a phosphorous ylide derived in situ from a suitable triphenyl-phosphonium-halogen salt. The desired carbonyl compound of formula (III) may be added to the in situ prepared phosphorous ylide.
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.
A solution of phenethyltriphenylphosphonium bromide (4.40 g, 9.84 mmol, 1.0 equiv.) in THF (20 mL) was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 6.2 mL, 9.84 mmol, 1.0 equiv.) at 0° C., the red solution was stirred at 60° C. for 1 h. The mixture was re-cooled to 0° C., 4-(2,6,6-trimethylcyclohex-1-enyl)butan-2-one (1.92 g, 9.84 mmol, 1.0 equiv.) in THF (10 mL) was added, and the mixture was stirred at 70° C. for 20 h. After addition of H2O, the aqueous layer was extracted with cyclohexane (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane) to yield 816 mg (29%) of the title compound as a colorless oil.
1H-NMR (CDCl3, 400 MHz): 7.32-7.27 (m, 2H), 7.22-7.17 (m, 3H), 5.41-5.37 (m, 0.5H), 5.33-5.30 (m, 0.5H), 3.39 (t, J=7.8 Hz, 2H), 2.22-2.16 (m, 1H), 2.13-2.08 (m, 3H), 1.93 (q, J=6.4 Hz, 2H), 1.82-1.81 (m, 1.5H), 1.78-1.77 (m, 1.5H), 1.67 (s, 1.5H), 1.62 (s, 1.5H), 1.61-1.55 (m, 2H), 1.46-1.41 (m, 2H), 1.04 (s, 3H), 1.01 (s, 3H).
MS (EI): 282 (M+, 6), 267 (1), 191 (12), 144 (11), 137 (100), 95 (67), 91 (33), 81 (42), 67 (10), 55 (9), 41 (18).
Following the general procedure as described in Examples 1 the following compounds have been prepared:
Starting from phenethyltriphenylphosphonium bromide (3.85 g, 8.61 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 5.4 mL, 8.61 mmol, 1.0 equiv.) and 3,7-dimethyloctanal (2.02 g, 12.9 mmol, 1.5 equiv.), 1.16 g (55%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
1H-NMR (CDCl3, 400 MHz): 7.31-7.28 (m, 2H), 7.21-7.18 (m, 3H), 5.65-5.50 (m, 2H), 3.42 (d, J=7.1 Hz, 1.7H), 3.36 (d, J=6.3 Hz, 0.3H), 2.20-1.84 (m, 2H), 1.59-1.49 (m, 2H), 1.37-1.26 (m, 3H), 1.19-1.16 (m, 3H), 0.95-0.85 (m, 9H).
MS (EI): 244 (M+, 17), 216 (1), 188 (1), 174 (5), 132 (8), 117 (41), 104 (100), 91 (67), 71 (47), 57 (67), 43 (46).
Starting from phenethyltriphenylphosphonium bromide (3.60 g, 8.05 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 5.0 mL, 8.05 mmol, 1.0 equiv.) and 2-methylundecanal (2.25 g, 12.1 mmol, 1.5 equiv.), 1.33 g (61%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (hexanes).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): honey, cistus, olibanum, floral.
1H-NMR (CDCl3, 400 MHz): 7.32-7.27 (m, 2H), 7.22-7.17 (m, 3H), 5.53-5.46 (m, 1H), 5.31-5.25 (m, 1H), 3.47-3.34 (m, 2H), 2.62-2.52 (m, 1H), 1.35-1.25 (m, 16H), 1.00 (d, J=6.8 Hz, 3H), 0.90 (t, J=6.8 Hz, 3H).
MS (EI): 272 (M+, 7), 180 (3), 160 (4), 145 (33), 129 (13), 117 (50), 104 (100), 97 (24), 91 (52), 83 (23), 69 (27), 55 (26), 41 (23).
Starting from phenethyltriphenylphosphonium bromide (3.67 g, 8.20 mmol, 1.0 equiv.), n-Bul_i (1.6 M in hexanes, 5.1 mL, 8.20 mmol, 1.0 equiv.) and 2,4-dimethylcyclohex-3-enecarbaldehyde (1.70 g, 12.3 mmol, 1.5 equiv.), 1.14 g (61%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
1H-NMR (CDCl3, 400 MHz): 7.32-7.28 (m, 2H), 7.22-7.18 (m, 3H), 5.63-5.22 (m, 3H), 3.50-3.36 (m, 2H), 2.33-2.29 (m, 0.2H), 2.23-2.15 (m, 0.8H), 2.10-2.01 (m, 1H), 1.96-1.90 (m, 2H), 1.73-1.65 (m, 4H), 1.54-1.43 (m, 1H), 0.97 (d, J=7.1 Hz, 2.6H), 0.92 (d, J=7.3 Hz, 0.4H).
MS (EI): 226 (M+, 20), 211 (2), 198 (9), 144 (27), 129 (100), 115 (23), 107 (17), 91 (47), 82 (93), 67 (49), 53 (8), 41 (14).
Starting from phenethyltriphenylphosphonium bromide (3.48 g, 7.78 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.9 mL, 7.78 mmol, 1.0 equiv.) and (E)-3,7-dimethylocta-2,6-dienal (1.78 g, 11.7 mmol, 1.5 equiv.), 0.54 g (29%) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
1H-NMR (CDCl3, 400 MHz): 7.32-7.28 (m, 2H), 7.24-7.19 (m, 3H), 6.68-6.64 (m, 0.1H), 6.39-6.31 (m, 0.9H), 6.26-6.23 (m, 0.7H), 5.92-5.85 (m, 0.3H), 5.76-5.48 (m, 1H), 5.18-5.11 (m, 1H), 3.56 (d, J=6.3 Hz, 1.3H), 3.47-3.43 (m, 0.7H), 2.22-2.11 (m, 4H), 1.87-1.76 (m, 3H), 1.73-1.71 (m, 3H), 1.66-1.63 (m, 3H).
MS (EI): 240 (M+, 5), 225 (1), 197 (2), 171 (10), 129 (18), 115 (11), 105 (4), 91 (100), 77 (5), 69 (13), 41 (14).
Starting from phenethyltriphenylphosphonium bromide (3.48 g, 7.78 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.9 mL, 7.78 mmol, 1.0 equiv.) and 3,7-dimethyloct-6-enal (1.80 g, 11.7 mmol, 1.5 equiv.), 0.97 g (51%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
1H-NMR (CDCl3, 400 MHz): 7.32-7.29 (m, 2H), 7.22-7.18 (m, 3H), 5.67-5.52 (m, 2H), 5.16-5.12 (m, 1H), 3.43 (d, J=7.1 Hz, 1.7H), 3.37 (d, J=6.3 Hz, 0.3H), 2.22-1.98 (m, 4H), 1.71 (d, J=1.0 Hz, 3H), 1.64-1.62 (m, 3H), 1.61-1.51 (m, 1H), 1.47-1.38 (m, 1H), 1.26-1.16 (m, 1H), 0.95 (d, J=6.6 Hz, 2.5H), 0.91 (d, J=6.8 Hz, 0.5H).
MS (EI): 242 (M+, 8), 227 (1), 199 (4), 157 (31), 138 (45), 129 (47), 117 (30), 109 (61), 91 (91), 81 (38), 69 (100), 55 (38), 41 (63).
Starting from phenethyltriphenylphosphonium bromide (5.00 g, 11.2 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 7.0 mL, 11.2 mmol, 1.0 equiv.) and 3-(3-isopropylphenyl)butanal (3.20 g, 16.8 mmol, 1.5 equiv.), 2.54 g (82%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, green, watery, syringe.
1H-NMR (CDCl3, 400 MHz): 7.33-7.14 (m, 5H), 7.09-7.05 (m, 4H), 5.58-5.44 (m, 2H), 3.32 (d, J=6.8 Hz, 1.6H), 3.28 (d, J=6.6 Hz, 0.4H), 2.91-2.85 (m, 1H), 2.82-2.75 (m, 1H), 2.47-2.38 (m, 2H), 1.29 (d, J=7.1 Hz, 3H), 1.25-1.23 (m, 6H).
MS (EI): 278 (M+, 7), 263 (1), 187 (2), 147 (100), 131 (8), 115 (7), 105 (19), 91 (22), 77 (5), 43 (13).
Starting from phenethyltriphenylphosphonium bromide (3.48 g, 7.78 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.9 mL, 7.78 mmol, 1.0 equiv.) and acetophenone (1.40 g, 11.7 mmol, 1.5 equiv.), 0.75 g (46%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
1H-NMR (CDCl3, 400 MHz): 7.42-7.13 (m, 10H), 5.97 (tq, J=7.4, 1.4 Hz, 0.25H), 5.65 (tq, J=7.6, 1.5 Hz, 0.75H), 3.57 (d, J=7.3 Hz, 0.5H), 3.32 (d, J=7.6 Hz, 1.5H), 2.14-2.14 (m, 0.75H), 2.08-2.07 (q, J=1.3 Hz, 2.25H).
MS (EI): 208 (M+, 67), 193 (56), 178 (28), 165 (11), 130 (24), 115 (100), 103 (10), 91 (42), 77 (17), 65 (12), 51 (12), 39 (5).
Starting from phenethyltriphenylphosphonium bromide (3.48 g, 7.78 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.9 mL, 7.78 mmol, 1.0 equiv.) and 6-methylhept-5-en-2-one (1.48 g, 11.7 mmol, 1.5 equiv.), 0.29 g (17%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
1H-NMR (CDCl3, 400 MHz): 7.31-7.27 (m, 2H), 7.21-7.17 (m, 3H), 5.39-5.34 (m, 1H), 5.19-5.11 (m, 1H), 3.38 (d, J=7.3 Hz, 2H), 2.20-2.06 (m, 4H), 1.77-1.76 (m, 1.7H), 1.73 (br. s, 1.3H), 1.71 (s, 3H), 1.64 (s, 1.7H), 1.62 (s, 1.3H).
MS (EI): 214 (M+, 11), 171 (17), 157 (9), 143 (37), 129 (57), 123 (23), 117 (29), 109 (6), 103 (14), 91 (57), 77 (13), 69 (100), 53 (11), 41 (71).
Starting from phenethyltriphenylphosphonium bromide (4.44 g, 9.93 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 6.3 mL, 10.1 mmol, 1.0 equiv.) and (E)-4-(2,6,6-trimethylcyclohex-1-enyl)but-3-en-2-one (2.86 g, 14.9 mmol, 1.5 equiv.), 1.69 g (61%) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 98:2).
1H-NMR (CDCl3, 400 MHz): 7.32-7.27 (m, 2H), 7.22-7.17 (m, 3H), 6.55 (d, J=16.2 Hz, 1H), 6.19 (d, J=16.2 Hz, 1H), 5.63-5.59 (m, 0.45H), 5.53-5.49 (m, 0.55H), 3.53 (d, J=7.6 Hz, 2H), 2.04-1.99 (m, 2H), 1.93-1.92 (m, 1.65H), 1.91-1.91 (m, 1.35H), 1.73 (d, J=1.0 Hz, 1.65H), 1.70 (s, 1.35H), 1.66-1.59 (m, 2H), 1.50-1.44 (m, 2H), 1.05 (s, 3H), 1.03 (s, 3H).
MS (EI): 280 (M+, 12), 265 (2), 237 (1), 189 (6), 133 (15), 119 (100), 105 (17), 91 (53), 77 (10), 65 (6), 55 (13), 41 (13).
Starting from phenethyltriphenylphosphonium bromide (1.82 g, 4.07 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 2.6 mL, 4.07 mmol, 1.0 equiv.) and 4-(benzo[d][1,3]dioxol-5-yl)butan-2-one (1.17 g, 6.10 mmol, 1.5 equiv.), 0.35 g (30%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 99:1).
1H-NMR (CDCl3, 400 MHz): 7.29-7.25 (m, 2H), 7.20-7.16 (m, 1H), 7.12-7.10 (m, 2H), 6.75-6.61 (m, 3H), 5.92 (s, 2H), 5.38-5.32 (m, 1H), 3.35 (d, J=7.3 Hz, 1H), 3.26 (d, J=7.3 Hz, 1H), 2.70-2.63 (m, 2H), 2.42-2.38 (m, 1H), 2.33-2.29 (m, 1H), 1.79-1.78 (m, 1.5H), 1.76-1.75 (m, 1.5H).
MS (EI): 280 (M+, 14), 135 (100), 128 (3), 115 (3), 105 (5), 91 (8), 77 (15), 65 (4), 51 (8).
Starting from phenethyltriphenylphosphonium bromide (2.80 g, 6.26 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.9 mL, 6.26 mmol, 1.0 equiv.) and (E)-3-methyl-4-(2,6,6-trimethylcyclohex-2-enyl)but-3-en-2-one (1.94 g, 9.39 mmol, 1.5 equiv.), 0.36 g (20%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 995:5).
1H-NMR (CDCl3, 400 MHz): 7.30-7.27 (m, 2H), 7.22-7.15 (m, 3H), 5.38-5.35 (m, 1H), 5.30-5.26 (m, 1H), 5.04-5.00 (m, 1H), 3.37 (d, J=7.3 Hz, 2H), 2.50 (d, J=10.9 Hz, 1H), 2.03-1.99 (m, 2H), 1.82-1.81 (m, 6H), 1.63-1.59 (m, 3H), 1.48-1.39 (m, 1H), 1.22-1.16 (m, 1H), 0.93 (s, 3H), 0.83 (s, 3H).
MS (EI): 294 (M+, 2), 238 (11), 223 (3), 171 (12), 147 (100), 119 (9), 105 (10), 91 (27), 77 (6), 65 (4), 55 (6), 41 (9).
Starting from phenethyltriphenylphosphonium bromide (3.05 g, 6.82 mmol, 1.0 equiv.), n-BuLi (1.6M in hexanes, 4.3 mL, 6.82 mmol, 1.0 equiv.) and (2E,6Z)-nona-2,6-dienal (1.41 g, 10.2 mmol, 1.5 equiv.), 0.94 g (61%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 995:5).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): green, fatty, watery, dark tea, nonadienal, floral, mimosa, cassie, violet.
1H-NMR (CDCl3, 400 MHz): 7.32-7.27 (m, 2H), 7.21-7.18 (m, 3H), 6.49-6.42 (m, 1H), 6.12-6.04 (m, 1H), 5.80-5.73 (m, 1H), 5.52-5.32 (m, 3H), 3.53 (d, J=7.6 Hz, 1.5H), 3.41 (d, J=6.8 Hz, 0.5H), 2.23-1.99 (m, 6H), 0.97 (t, J=7.6 Hz, 2.25H), 0.96 (t, J=7.3 Hz, 0.75H).
MS (EI): 226 (M+, 2), 211 (1), 197 (3), 157 (8), 129 (15), 115 (17), 91 (100), 79 (8), 65 (5), 41 (11).
Starting from phenethyltriphenylphosphonium bromide (3.20 g, 7.15 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.5 mL, 7.15 mmol, 1.0 equiv.) and (E)-dec-4-enal (1.66 g, 10.7 mmol, 1.5 equiv.), 1.08 g (62%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): aldehydic, green, honey, floral, citrus.
1H-NMR (CDCl3, 400 MHz): 7.31-7.27 (m, 2H), 7.21-7.17 (m, 3H), 5.61-5.51 (m, 2H), 5.46-5.39 (m, 2H), 3.41 (d, J=6.6 Hz, 1.7H), 3.34 (d, J=6.1 Hz, 0.3H), 2.26-1.95 (m, 6H), 1.39-1.23 (m, 6H), 0.90 (t, J=7.0 Hz, 3H).
MS (EI): 242 (M+, 2), 171 (5), 158 (17), 138 (35), 130 (100), 115 (31), 104 (25), 91 (96), 82 (26), 69 (74), 55 (53), 41 (44).
Starting from phenethyltriphenylphosphonium bromide (2.30 g, 5.14 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.2 mL, 5.14 mmol, 1.0 equiv.) and 1-(naphthalen-2-yl)ethanone (1.22 g, 7.20 mmol, 1.4 equiv.), 0.71 g (54%) of the title compound as a yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 995:5).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, honey, orange flower, mimosa, acacia.
1H-NMR (CDCl3, 400 MHz): 7.86-7.17 (m, 12H), 6.18-6.13 (m, 0.35H), 5.79-5.75 (m, 0.65H), 3.65 (d, J=7.3 Hz, 0.7H), 3.39 (d, J=7.3 Hz, 1.3H), 2.28-2.27 (m, 1.05H), 2.19-2.18 (m, 1.95H).
MS (EI): 258 (M+, 94), 243 (65), 228 (20), 215 (12), 180 (27), 165 (100), 152 (30), 141 (16), 128 (28), 115 (68), 91 (52), 77 (13), 65 (6), 51 (11).
Starting from phenethyltriphenylphosphonium bromide (3.20 g, 7.15 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.5 mL, 7.15 mmol, 1.0 equiv.) and 2,6-dimethylhept-5-enal (1.51 g, 10.7 mmol, 1.5 equiv.), 1.21 g (74%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
1H-NMR (CDCl3, 400 MHz): 7.31-7.28 (m, 2H), 7.21-7.18 (m, 3H), 5.57-5.48 (m, 1H), 5.42-5.26 (m, 1H), 5.15-5.09 (m, 1H), 3.47-3.34 (m, 2H), 2.63-2.55 (m, 1H), 2.04-1.93 (m, 2H), 1.70 (d, J=1.3 Hz, 3H), 1.61 (s, 3H), 1.35-1.25 (m, 2H), 1.01 (d, J=6.6 Hz, 3H).
MS (EI): 228 (M+, 7), 213 (1), 185 (21), 157 (16), 143 (39), 137 (20), 129 (42), 117 (38), 109 (41), 104 (20), 91 (100), 81 (64), 69 (52), 55 (59), 41 (70).
Starting from phenethyltriphenylphosphonium bromide (3.16 g, 7.06 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.4 mL, 7.06 mmol, 1.0 equiv.) and 4-methoxybenzaldehyde (1.44 g, 10.6 mmol, 1.5 equiv.), 1.36 g (86%) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 99:1).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, aldehydic, anisic like, and honey, linden blossom.
1H-NMR (CDCl3, 400 MHz): 7.36-7.21 (m, 7H), 6.95-6.83 (m, 2H), 6.57-6.53 (m, 0.25H), 6.44-6.40 (m, 0.75H), 6.27-6.20 (m, 0.75H), 5.83-5.76 (m, 0.25H), 3.83 (s, 0.75H), 3.81 (s, 2.25H), 3.70 (dd, J=7.5, 1.4 Hz, 0.5H), 3.55 (d, J=7.1 Hz, 1.5H).
MS (EI): 224 (M+, 100), 209 (23), 193 (31), 178 (20), 165 (20), 121 (24), 115 (365), 103 (13), 91 (32), 77 (20), 65 (11), 51 (13).
Starting from phenethyltriphenylphosphonium bromide (3.00 g, 6.71 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.2 mL, 6.71 mmol, 1.0 equiv.) and 3-(4-tert-butylphenyl)-2-methylpropanal (2.05 g, 10.1 mmol, 1.5 equiv.), 1.35 g (69%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, green, muguet, watery, lilial like, and green, honey, aldehydic, syringe.
1H-NMR (CDCl3, 400 MHz): 7.33-6.99 (m, 9H), 5.62-5.59 (m, 0.1H), 5.49-5.47 (m, 0.1H), 5.46-5.39 (m, 0.9H), 5.36-5.31 (m, 0.9H), 3.31-3.13 (m, 2H), 2.89-2.80 (m, 1H), 2.62-2.54 (m, 2H), 1.31 (s, 9H), 1.03 (d, J=6.6 Hz, 3H).
MS (EI): 292 (M+, 8), 277 (3), 235 (4), 201 (8), 147 (100), 132 (19), 117 (44), 105 (15), 91 (39), 77 (6), 57 (33), 41 (11).
Starting from phenethyltriphenylphosphonium bromide (2.23 g, 4.98 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.1 mL, 4.98 mmol, 1.0 equiv.) and 3-(4-ethylphenyl)-2,2-dimethylpropanal (1.42 g, 7.48 mmol, 1.5 equiv.), 0.71 g (51%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
1H-NMR (CDCl3, 400 MHz): 7.30-7.10 (m, 9H), 5.47-5.38 (m, 2H), 3.44 (d, J=4.6 Hz, 1.4H), 3.39 (d, J=5.8 Hz, 0.6H), 2.81-2.63 (m, 4H), 1.28-1.18 (m, 9H).
MS (EI): 278 (M+, 2), 187 (39), 159 (77), 143 (20), 129 (14), 117 (100), 103 (10), 91 (54), 77 (10), 65 (8), 43 (9).
Starting from phenethyltriphenylphosphonium bromide (2.80 g, 6.26 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.9 mL, 6.26 mmol, 1.0 equiv.) and 3,5,5-trimethylhexanal (1.33 g, 9.39 mmol, 1.5 equiv.), 0.94 g (65%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): natural honey, woody aspects, dry strawberry aspects.
1H-NMR (CDCl3, 400 MHz): 7.31-7.28 (m, 2H), 7.21-7.18 (m, 3H), 5.66-5.46 (m, 2H), 3.41 (d, J=7.1 Hz, 1.7H), 3.36 (d, J=6.3 Hz, 0.3H), 2.19-1.98 (m, 2H), 1.68-1.57 (m, 1H), 1.36-1.27 (m, 1H), 1.14-1.05 (m, 1H), 1.00-0.85 (m, 12H).
MS (EI): 230 (M+, 6), 174 (12), 132 (4), 117 (14), 104 (20), 91 (30), 57 (100), 41 (14).
Starting from phenethyltriphenylphosphonium bromide (2.20 g, 4.92 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.1 mL, 4.92 mmol, 1.0 equiv.) and 4-(6-methylheptan-2-yloxy)butanal (0.86 g, 4.29 mmol, 0.9 equiv.), 0.42 g (27%) of the title compound as a yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
1H-NMR (CDCl3, 400 MHz): 7.31-7.28 (m, 2H), 7.20-7.17 (m, 3H), 5.62-5.51 (m, 2H), 3.54-3.34 (m, 5H), 2.27-2.21 (m, 2H), 1.71-1.64 (m, 2H), 1.55-1.49 (m, 2H), 1.40-1.26 (m, 3H), 1.20-1.15 (m, 2H), 1.13 (d, J=6.1 Hz, 3H), 0.87 (d, J=6.6 Hz, 6H).
MS (EI): 288 (M+, 1), 273 (1), 203 (8), 176 (6), 158 (31), 143 (24), 129 (73), 117 (67), 104 (17), 91 (100), 71 (40), 57 (56), 43 (40).
Starting from phenethyltriphenylphosphonium bromide (2.60 g, 5.81 mmol, 1.0 equiv.), n-BuLi (1.3 M in hexanes, 4.5 mL, 5.81 mmol, 1.0 equiv.) and 3-(3-tert-butylcyclohexyl)propanal (1.45 g, 7.39 mmol, 1.3 equiv.), 1.01 g (61%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
1H-NMR (CDCl3, 400 MHz): 7.31-7.28 (m, 2H), 7.21-7.17 (m, 3H), 5.61-5.48 (m, 2H),
3.42 (d, J=6.1 Hz, 1.7H), 3.34 (d, J=6.1 Hz, 0.3H), 2.24-2.04 (m, 2H), 1.83-1.73 (m, 4H), 1.49-1.15 (m, 4H), 1.02-0.54 (m, 13H).
MS (EI): 284 (M+, 1), 269 (1), 227 (35), 192 (6), 145 (11), 137 (13), 131 (47), 117 (31), 104 (43), 91 (100), 81 (38), 67 (25), 57 (92), 41 (37).
Starting from phenethyltriphenylphosphonium bromide (2.00 g, 4.47 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 2.8 mL, 4.47 mmol, 1.0 equiv.) and 2-(4-tert-pentylcyclohexyl)acetaldehyde (1.32 g, 6.71 mmol, 1.5 equiv.), 0.62 g (48%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
1H-NMR (CDCl3, 400 MHz): 7.33-7.28 (m, 2H), 7.22-7.17 (m, 3H), 5.63-5.48 (m, 2H), 3.44-3.34 (m, 2H), 2.21-2.02 (m, 2H), 1.91-1.64 (m, 4H), 1.49-1.41 (m, 2H), 1.30-1.20 (m, 2H), 1.18-0.88 (m, 4H), 0.81-0.74 (m, 9H).
MS (EI): 284 (M+, 4), 269 (1), 255 (11), 214 (11), 131 (21), 117 (26), 104 (33), 97 (23), 91 (51), 83 (17), 71 (100), 55 (28), 43 (47).
a) Phenethyltriphenylphosphonium bromide (4.74 g, 10.6 mmol, 1.0 equiv.) in THF (20 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 6.6 mL, 10.6 mmol, 1.0 equiv.) at 0° C., the red solution was stirred at 70° C. for 1 h. The mixture was re-cooled to 0° C., 4-(tert-butyldimethylsilyloxy)-3-ethoxybenzaldehyde) (2.98 g, 10.6 mmol, 1.0 equiv.) in THF (10 mL) was added, and the mixture was stirred at 70° C. for 14 h. After addition of H2O, the aqueous layer was extracted with cyclohexane (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 98:2) to yield 3.12 g (80%) of a yellow oil, containing tert-butyl(2-ethoxy-4-(3-phenylprop-1-enyl)phenoxy)-dimethylsilane.
b) To a solution of tert-butyl(2-ethoxy-4-(3-phenylprop-1-enyl)phenoxy)-dimethylsilane (3.12 g, 8.46 mmol, 1.0 equiv.), in THF (17 mL), n-Bu4NF (10.2 mL, 10.2 mmol, 1.2 equiv., 1.0 M in THF) was added, and the mixture was stirred at 25° C. for 1 h. After addition of H2O, the aqueous layer was extracted with MTBE (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 95:5) to yield 1.60 g (74%) of the title compound as a yellow oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, spicy, vanilla, green, honey.
1H-NMR (CDCl3, 400 MHz): 7.36-7.30 (m, 2H), 7.28-7.23 (m, 3H), 6.98-6.79 (m, 3H), 6.54-6.50 (m, 0.4H), 6.40-6.35 (m, 0.6H), 6.22-6.15 (m, 0.6H), 5.82-5.75 (m, 0.4H), 5.70 (s, 0.4H), 5.68 (s, 0.6H), 4.11 (q, J=7.1 Hz, 1.2H), 4.05 (q, J=7.0 Hz, 0.8H), 3.69 (dd, J=7.6, 1.3 Hz, 0.8H), 3.53 (d, J=6.8 Hz, 1.2H), 1.44 (t, J=7.1 Hz, 1.8H), 1.42 (t, J=7.1 Hz, 1.2H).
MS (EI): 254 (M+, 100), 237 (2), 225 (26), 207 (23), 197 (10), 179 (26), 165 (17), 152 (11), 131 (13), 115 (46), 103 (13), 91 (41), 77 (15), 65 (11).
Following the general procedure as described in Example 3 the following compounds have been prepared:
a) First starting from phenethyltriphenylphosphonium bromide (5.27 g, 11.8 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 7.4 mL, 11.8 mmol, 1.0 equiv.) and 4-(4-(tert-butyldimethylsilyloxy)phenyl)butan-2-one (3.94 g, 14.1 mmol, 1.2 equiv.), 1.86 g (43%) of a light yellow oil, containing tert-butyldimethyl(4-(3-methyl-5-phenylpent-3-enyl)phenoxy)silane, was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 99:1).
b) Starting from tert-butyldimethyl(4-(3-methyl-5-phenylpent-3-enyl)phenoxy)silane (1.86 g, 5.07 mmol, 1.0 equiv.) and n-Bu4NF (6.1 mL, 6.09 mmol, 1.2 equiv., 1.0 M in THF), 0.78 g (61%) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 95:5→9:1).
1H-NMR (CDCl3, 400 MHz): 7.33-7.28 (m, 2H), 7.24-7.19 (m, 1H), 7.16-7.06 (m, 4H), 6.80-6.75 (m, 2H), 5.41-5.35 (m, 1H), 4.92 (d, J=7.6 Hz, 1H), 3.39 (d, J=7.3 Hz, 1H), 3.28 (d, J=7.3 Hz, 1H), 2.74-2.68 (m, 2H), 2.46-2.42 (m, 1H), 2.37-2.33 (m, 1H), 1.82 (q, J=1.8 Hz, 1.5H), 1.79 (d, J=0.5 Hz, 1.5H).
MS (EI): 252 (M+, 11), 145 (4), 129 (5), 107 (100), 103 (2), 91 (9), 77 (10).
a) Starting from p-methylphenethyltriphenylphosphonium bromide (3.90 g, 8.45 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 5.3 mL, 8.45 mmol, 1.0 equiv.) and 4-(tert-butyldimethylsilyloxy)-3-ethoxybenzaldehyde (2.37 g, 8.45 mmol, 1.0 equiv.), 2.72 g (84%) of a light yellow oil, containing (E)-tert-butyl(2-ethoxy-4-(3-p-tolylprop-1-enyl)phenoxy)dimethylsilane, was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 997:3).
b) Starting from (E)-tert-butyl(2-ethoxy-4-(3-p-tolylprop-1-enyl)phenoxy)dimethylsilane (2.72 g, 7.11 mmol, 1.0 equiv.) and n-Bu4NF (8.5 mL, 8.53 mmol, 1.2 equiv., 1.0 M in THF), 1.53 g (80%) of the title compound as a viscous yellow oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 19:1→9:1).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): powdery vanilla, floral, slightly spicy, carnation.
1H-NMR (CDCl3, 400 MHz): 7.19-7.09 (m, 4H), 6.95-6.81 (m, 3H), 6.51-6.48 (m, 0.35H), 6.39-6.34 (m, 0.65H), 6.21-6.13 (m, 0.65H), 5.80-5.74 (m, 0.35H), 5.66 (s, 0.35H), 5.63 (s, 0.65H), 4.11 (q, J=7.1 Hz, 1.3H), 4.06 (q, J=7.1 Hz, 0.7H), 3.65 (dd, J=7.5, 1.4 Hz, 0.7H), 3.49 (dd, J=7.1, 1.0 Hz, 1.3H), 2.34 (s, 3H), 1.47-1.41 (m, 3H).
MS (EI): 268 (M+, 100), 253 (9), 239 (19), 223 (17), 207 (20), 193 (15), 178 (22), 165 (18), 152 (12), 129 (32), 115 (26), 105 (30), 91 (23), 77 (17), 65 (11), 55 (10), 29 (14).
a) First starting from p-methoxyphenethyltriphenylphosphonium bromide (3.90 g, 8.17 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 5.1 mL, 8.17 mmol, 1.0 equiv.) and 4-(tert-butyldimethylsilyloxy)-3-ethoxybenzaldehyde (2.29 g, 8.17 mmol, 1.0 equiv.), 2.50 g (77%) of a yellow oil, containing (E)-tert-butyl(2-ethoxy-4-(3-(4-methoxyphenyl)prop-1-enyl)phenoxy)dimethylsilane, was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 99:1).
b) Then, starting from (E)-tert-butyl(2-ethoxy-4-(3-(4-methoxyphenyl)prop-1-enyl)phenoxy)dimethylsilane (2.50 g, 6.27 mmol, 1.0 equiv.) and n-Bu4NF (7.5 mL, 7.53 mmol, 1.2 equiv., 1.0 M in THF), 1.25 g (70%) of the title compound as a viscous yellow oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 19:1→9:1).
1H-NMR (CDCl3, 400 MHz): 7.19-7.13 (m, 2H), 6.95-6.81 (m, 5H), 6.51-6.47 (m, 0.35H), 6.37-6.33 (m, 0.65H), 6.20-6.13 (m, 0.65H), 5.79-5.72 (m, 0.35H), 5.67 (s, 0.35H), 5.64 (s, 0.65H), 4.11 (q, J=6.8 Hz, 1.3H), 4.06 (q, J=7.1 Hz, 0.7H), 3.80-3.80 (m, 3H), 3.63 (dd, J=7.3, 1.5 Hz, 0.7H), 3.47 (d, J=6.6 Hz, 1.3H), 1.47-1.41 (m, 3H).
MS (EI): 284 (M+, 100), 267 (5), 255 (22), 239 (19), 227 (11), 209 (11), 195 (9), 165 (18), 145 (35), 134 (18), 121 (45), 115 (19), 103 (10), 91 (23), 77 (22), 65 (10), 55 (11), 29 (16).
p-Methoxyphenethyltriphenylphosphonium bromide (3.40 g, 7.12 mmol, 1.0 equiv.) in THF (14 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 4.5 mL, 7.12 mmol, 1.0 equiv.) at 0° C., the red solution was stirred at 65° C. for 1 h. The mixture was re-cooled to 0° C., 2-methylundecanal (1.97 g, 10.7 mmol, 1.5 equiv.) in THF (6 mL) was added, and the mixture was stirred at 70° C. for 14 h. After addition of H2O, the aqueous layer was extracted with cyclohexane (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 98:2) to yield 1.36 g (63%) of the title compound as a light yellow oil.
1H-NMR (CDCl3, 400 MHz): 7.13-7.09 (m, 2H), 6.85-6.82 (m, 2H), 5.49-5.43 (m, 1H), 5.28-5.22 (m, 1H), 3.79 (s, 3H), 3.40-3.26 (m, 2H), 2.58-2.50 (m, 1H), 1.33-1.25 (m, 16H), 0.98 (d, J=6.6 Hz, 3H), 0.89 (t, J=6.8 Hz, 3H).
MS (EI): 302 (M+, 13), 194 (3), 175 (10), 147 (100), 134 (50), 121 (71), 108 (11), 91 (9), 82 (10), 67 (5), 55 (9), 41 (12).
Following the general procedure as described in Example 5 the following compounds have been prepared:
Starting from p-methoxyphenethyltriphenylphosphonium bromide (1.20 g, 2.51 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 1.6 mL, 2.51 mmol, 1.0 equiv.) and 3-(3-isopropylphenyl)butanal (0.72 g, 3.77 mmol, 1.5 equiv.), 0.20 g (26%) of the title compound as a yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 99:1).
1H-NMR (CDCl3, 400 MHz): 7.25-7.21 (m, 1H), 7.10-6.98 (m, 5H), 6.83-6.79 (m, 2H), 5.55-5.43 (m, 2H), 3.79 (s, 3H), 3.27 (d, J=7.1 Hz, 1.6H), 3.23 (d, J=6.3 Hz, 0.4H), 2.93-2.86 (m, 1H), 2.83-2.76 (m, 1H), 2.47-2.37 (m, 2H), 1.31 (d, J=7.1 Hz, 3H), 1.27-1.22 (m, 6H).
MS (EI): 308 (M+, 16), 161 (9), 147 (100), 131 (6), 121 (19), 105 (21), 91 (17), 77 (16), 43 (19).
Starting from p-methoxyphenethyltriphenylphosphonium bromide (3.12 g, 6.54 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.1 mL, 6.54 mmol, 1.0 equiv.) and (E)-dec-4-enal (1.51 g, 9.80 mmol, 1.5 equiv.), 0.85 g (48%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 992:8).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): aldehydic, green, watery, floral, anisic.
1H-NMR (CDCl3, 400 MHz): 7.13-7.09 (m, 2H), 6.85-6.81 (m, 2H), 5.56-5.39 (m, 4H), 3.79 (s, 3H), 3.34 (d, J=6.6 Hz, 1.7H), 3.27 (d, J=5.8 Hz, 0.3H), 2.22-1.96 (m, 6H), 1.35-1.25 (m, 6H), 0.91-0.87 (m, 3H).
MS (EI): 272 (M+, 7), 173 (7), 161 (32), 147 (19), 134 (100), 129 (14), 121 (51), 91 (21), 77 (9), 69 (11), 55 (16), 41 (21).
Starting from p-methoxyphenethyltriphenylphosphonium bromide (3.15 g, 6.60 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.2 mL, 6.60 mmol, 1.0 equiv.) and 1-(naphthalen-2-yl)ethanone (1.69 g, 9.90 mmol, 1.5 equiv.), 0.92 g (48%) of the title compound as a yellow oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 995:5→99:1).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, orange flower, natural, cassie.
1H-NMR (CDCl3, 400 MHz): 7.86-7.39 (m, 7H), 7.23-7.19 (m, 0.8H), 7.11-7.07 (m, 1.2H), 6.90-6.82 (m, 2H), 6.16-6.11 (m, 0.4H), 5.77-5.72 (m, 0.6H), 3.81 (s, 1.2H), 3.80 (s, 1.8H), 3.59 (d, J=7.3 Hz, 0.8H), 3.33 (d, J=7.3 Hz, 1.2H), 2.27-2.26 (m, 1.2H), 2.18-2.17 (m, 1.8H).
MS (EI): 288 (M+, 79), 273 (55), 258 (8), 215 (12), 180 (39), 165 (100), 152 (27), 145 (48), 128 (20), 121 (54), 115 (22), 91 (16), 77 (15), 65 (7), 51 (7).
Starting from p-methoxyphenethyltriphenylphosphonium bromide (3.10 g, 6.49 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 4.1 mL, 6.49 mmol, 1.0 equiv.) and 3-(4-tert-butylphenyl)-2-methylpropanal (1.99 g, 9.74 mmol, 1.5 equiv.), 1.07 g (44%) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
1H-NMR (CDCl3, 400 MHz): 7.32-7.29 (m, 2H), 7.13-7.10 (m, 2H), 6.94-6.91 (m, 2H), 6.79-6.76 (m, 2H), 5.47-5.31 (m, 2H), 3.77 (s, 3H), 3.23-3.09 (m, 2H), 2.90-2.83 (m, 1H), 2.60-2.57 (m, 2H), 1.33 (s, 9H), 1.04 (d, J=6.6 Hz, 3H).
MS (EI): 322 (M+, 26), 201 (34), 175 (100), 160 (12), 147 (83), 134 (25), 121 (100), 105 (12), 91 (26), 77 (9), 57 (14), 41 (11).
1-Methyl-4-(4-methyltridec-2-enyl)benzene
p-Methylphenethyltriphenylphosphonium bromide (2.90 g, 6.29 mmol, 1.0 equiv.) in THF (12 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 3.9 mL, 6.29 mmol, 1.0 equiv.) at 0° C., the red solution was stirred at 65° C. for 1 h. The mixture was re-cooled to 0° C., 2-methylundecanal (1.74 g, 9.43 mmol, 1.5 equiv.) in THF (5 mL) was added, and the mixture was stirred at 65° C. for 16 h. After addition of H2O, the aqueous layer was extracted with cyclohexane (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3) to yield 1.24 g (69%) of the title compound as a colorless oil.
Odor description (dry-down after 24 hours on a smelling strip): fresh, clean, aldehydic, resinous.
1H-NMR (CDCl3, 400 MHz): 7.13-7.07 (m, 4H), 5.50-5.44 (m, 1H), 5.29-5.23 (m, 1H), 3.42-3.29 (m, 2H), 2.57-2.53 (m, 1H), 2.32 (s, 3H), 1.33-1.21 (m, 16H), 0.98 (d, J=6.8 Hz, 3H), 0.91-0.87 (m, 3H).
MS (EI): 286 (M+, 8), 159 (21), 131 (82), 118 (100), 105 (62), 91 (9), 83 (7), 69 (14), 55 (18), 41 (21).
Following the general procedure as described in Example 7 the following compounds have been prepared:
Starting from p-methylphenethyltriphenylphosphonium bromide (2.90 g, 6.29 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.9 mL, 6.29 mmol, 1.0 equiv.) and (E)-dec-4-enal (1.45 g, 9.43 mmol, 1.5 equiv.), 0.92 g (57%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): aldehydic, green, sharp, watery.
1H-NMR (CDCl3, 400 MHz): 7.13-7.07 (m, 4H), 5.60-5.40 (m, 4H), 3.37 (d, J=6.8 Hz, 1.7H), 3.30 (d, J=6.1 Hz, 0.3H), 2.33 (s, 3H), 2.25-1.98 (m, 6H), 1.39-1.25 (m, 6H), 0.92-0.88 (m, 3H).
MS (EI): 256 (M+, 2), 241 (1), 185 (3), 145 (58), 129 (45), 118 (100), 105 (58), 91 (17), 79 (11), 69 (22), 55 (22), 41 (26).
Starting from p-methylphenethyltriphenylphosphonium bromide (5.04 g, 9.91 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 6.2 mL, 9.91 mmol, 1.0 equiv.) and 3-(4-tert-butylphenyl)-2-methylpropanal (3.04 g, 14.9 mmol, 1.5 equiv.), 1.26 g (42%) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
1H-NMR (CDCl3, 400 MHz): 7.34-7.30 (m, 2H), 7.15-7.11 (m, 2H), 7.07 (d, J=7.8 Hz, 2H), 6.94 (d, J=8.0 Hz, 2H), 5.51-5.33 (m, 2H), 3.31-3.13 (m, 2H), 2.93-2.86 (m, 1H), 2.62-2.55 (m, 2H), 2.33 (s, 3H), 1.36 (s, 9H), 1.06 (d, J=6.7 Hz, 3H).
MS (EI): 306 (M+, 16), 291 (2), 249 (2), 201 (11), 159 (95), 147 (100), 131 (36), 117 (44), 105 (50), 91 (28), 77 (9), 57 (55), 41 (13).
Starting from p-methylphenethyltriphenylphosphonium iodide, which has been synthesized from 1-(2-iodoethyl)-4-methylbenzene and PPh3, (2.54 g, 5.00 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.1 mL, 5.00 mmol, 1.0 equiv.) and benzo[d][1,3]dioxole-5-carbaldehyde (0.98 g, 6.50 mmol, 1.3 equiv.), 0.50 g (40%) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
1H-NMR (CDCl3, 400 MHz): 7.14-7.11 (m, 4H), 6.91-6.73 (m, 3H), 6.48 (dt, J=11.5, 1.6 Hz, 0.3H), 6.37 (d, J=15.7 Hz, 0.7H), 6.18 (dt, J=15.7, 6.8 Hz, 0.7H), 5.96 (s, 0.6H), 5.94 (s, 1.4H), 5.77 (dt, J=11.4, 7.6 Hz, 0.3H), 3.63 (dd, J=7.5, 1.6 Hz, 0.6H), 3.49 (dd, J=6.9, 1.1 Hz, 1.4H), 2.34 (s, 3H).
MS (EI): 252 (M+, 100), 237 (31), 222 (20), 207 (35), 193 (12), 179 (38), 165 (12), 152 (11), 135 (13), 129 (14), 115 (27), 103 (20), 89 (18), 77 (26), 63 (12), 51 (12).
A solution of naphthaleneethyltriphenylphosphonium bromide which has been synthesized from 2-(2-bromoethyl)-2-naphthalene and PPh3, (3.36 g, 6.76 mmol, 1.0 equiv.) in THF (14 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 4.2 mL, 6.76 mmol, 1.0 equiv.) at 0° C., the red-brown suspension was stirred at 65° C. for 1 h. The mixture was re-cooled to 0° C., 2-methylundecanal (1.87 g, 10.1 mmol, 1.5 equiv.) in THF (5 mL) was added, and the mixture was stirred at 65° C. for 16 h. After addition of H2O, the aqueous layer was extracted with cyclohexane (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane) to yield 0.31 g (14%) of the title compound as a light yellow oil.
1H-NMR (CDCl3, 400 MHz): 7.84-7.35 (m, 7H), 7.37-7.35 (m, 1H), 5.63-5.57 (m, 1H), 5.39-5.33 (m, 1H), 3.64-3.51 (m, 2H), 2.68-2.60 (m, 1H), 1.39-1.25 (m, 16H), 1.04 (d, J=6.6 Hz, 3H), 0.91 (t, J=6.8 Hz, 3H).
MS (EI): 322 (M+, 26), 196 (2), 179 (18), 167 (73), 154 (100), 141 (90), 128 (50), 115 (14), 95 (11), 82 (17), 69 (12), 55 (20), 43 (22).
A suspension of benzyltriphenylphosphonium bromide (3.20 g, 7.38 mmol, 1.0 equiv.) in THF (14 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 4.6 mL, 7.38 mmol, 1.0 equiv.) at 0° C., the red suspension was stirred at 65° C. for 1 h. The mixture was re-cooled to 0° C., 2-methylundecanal (2.04 g, 11.1 mmol, 1.5 equiv.) in THF (5 mL) was added, and the mixture was stirred at 65° C. for 18 h. After addition of H2O, the aqueous layer was extracted with cyclohexane (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane) to yield 1.45 g (76%) of the title compound as a colorless oil.
1H-NMR (CDCl3, 400 MHz): 7.37-7.17 (m, 5H), 6.39-6.32 (m, 1H), 6.10 (dd, J=15.9, 7.8 Hz, 0.7H), 6.10 (dd, J=11.6, 10.4 Hz, 0.3H), 2.79-2.69 (m, 0.3H), 2.34-2.24 (m, 0.7H), 1.41-1.23 (m, 16H), 1.08 (d, J=6.8 Hz, 2.1H), 1.04 (d, J=6.6 Hz, 0.9H), 0.89 (t, J=6.8 Hz, 3H).
MS (EI): 258 (M+, 7), 243 (1), 131 (100), 115 (8), 104 (26), 91 (26), 55 (4), 41 (8).
To a suspension of benzyltriphenylphosphonium bromide (10.9 g, 25.1 mmol, 1.2 equiv.) in THF (35 mL), was added potassium-f-amylat (1.7 M in toluene, 20 mL, 34.0 mmol, 1.7 equiv.) at 25° C. 4-(4-Hydroxyphenyl)butan-2-one (3.3 g, 20.1 mmol, 1.0 equiv.) in THF (5 mL) was added to the red suspension, and the mixture was stirred at 70° C. for 30 min. After addition of 20% aq. AcOH-solution (10 mL) at 25° C., the aqueous layer was diluted with hexanes (50 mL). The organic phase was washed with H2O (2×30 mL) and MeOH/H2O (8:2, 2×20 mL) and concentrated. The residue was purified by flash chromatography on SiO2 to yield 2.10 g (44%) of the title compound as a white solid.
1H-NMR (CDCl3, 400 MHz): 7.31-7.25 (m, 2H), 7.20-7.11 (m, 3H), 7.07-7.04 (m, 1.2H), 7.00-6.97 (m, 0.8H), 6.75-6.68 (m, 2H), 6.31 (s, 0.4H), 6.23 (s, 0.6H), 5.09 (s, 1H), 2.76-2.69 (m, 2H), 2.49-2.45 (m, 0.8H), 2.43-2.39 (m, 1.2H), 1.91 (d, J=1.3 Hz, 1.2H), 1.87 (d, J=1.3 Hz, 1.8H).
MS (EI): 238 (M+, 9), 131 (23), 115 (11), 107 (100), 91 (17), 77 (13).
a) To a solution of 4-(tert-butyldimethylsilyloxy)-3-ethoxybenzaldehyde (12.7 g, 45.4 mmol, 1.0 equiv.) in EtOH (50 mL), NaBH4 (868 mg, 22.7 mmol, 0.5 equiv.) was added at 0° C., and the mixture was stirred at 0° C. for 2 h. After slow addition of sat. aq. NaHCO3-solution, the aqueous layer was extracted with EtOAc (2×). The combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated to yield 12.6 g (98%) of (4-(tert-butyldimethylsilyloxy)-3-ethoxyphenyl)methanol as a light yellow oil.
b) To a solution of (4-(tert-butyldimethylsilyloxy)-3-ethoxyphenyl)methanol (12.5 g, 44.4 mmol, 1.0 equiv.) in CH2CI2 (45 mL), PBr3 (5.0 mL, 53.2 mmol, 1.2 equiv.) was added at 0° C., and the mixture was stirred at 0° C. for 30 min. After slow addition of sat. aq. NaHCO3-solution, the aqueous layer was extracted with CH2Cl2 (2×). The combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated to yield 14.5 g (94%) of (4-(bromomethyl)-2-ethoxyphenoxy)(tert-butyl)dimethylsilane as a light yellow oil.
c) To a solution of (4-(bromomethyl)-2-ethoxyphenoxy)(tert-butyl)dimethylsilane (14.5 g, 41.8 mmol, 1.0 equiv.) in toluene (84 mL), PPh3 (11.0 g, 41.8 mmol, 1.0 equiv.) was added. The mixture was stirred at 25° C. for 20 h and concentrated to yield 25.1 g (99%) of (4-(tert-Butyldimethylsilyloxy)-3-ethoxyphenyl)methyltriphenylphosphonium bromide as a white solid.
d) A solution of (4-(tert-Butyldimethylsilyloxy)-3-ethoxyphenyl)methyltriphenyl-phosphonium bromide (28.7 g, 41.6 mmol, 1.0 equiv.) in THF (90 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 26 mL, 41.6 mmol, 1.0 equiv.) at 0° C., the red suspension was stirred at 0° C. for 15 min. 4-(4-(Tert-butyldimethylsilyloxy)phenyl)butan-2-one (12.9 g, 41.6 mmol, 1.0 equiv.) in THF (30 mL) was added, and the mixture was stirred at 0° C.→70° C. for 16 h. After addition of H2O at 25° C., the aqueous layer was extracted with hexanes (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 98:2) to give tert-butyl(4-(4-(4-((tert-butyldimethylsilyl)oxy)-3-ethoxyphenyl)-3-methylbut-3-en-1-yl)phenoxy)dimethylsilane as a colorless oil.
e) tert-Butyl(4-(4-(4-((tert-butyldimethylsilyl)oxy)-3-ethoxyphenyl)-3-methylbut-3-en-1-yl)phenoxy)dimethylsilane was dissolved in THF (30 mL), n-Bu4NF (30 mL, 30.0 mmol, 0.7 equiv., 1.0 M in THF) was added, and the mixture was stirred at 25° C. for 1 h. After addition of H2O, the aqueous layer was extracted with MTBE (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 9:1→4:1) to yield 5.87 g (48% over 2 steps) of the title compound as a light yellow oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): sweet, raspberry, vanillin, plumy.
1H-NMR (CDCl3, 400 MHz): 7.10-7.07 (m, 1.12H), 7.04-7.00 (m, 0.88H), 6.88 (d, J=8.1 Hz, 0.56H), 6.85 (d, J=8.1 Hz, 0.44H), 6.79-6.61 (m, 4H), 6.24 (s, 0.44H), 6.17 (s, 0.56H), 5.64 (s, 0.56H), 5.63 (s, 0.44H), 4.82 (d, J=2.0 Hz, 1H), 4.11 (q, J=7.0 Hz, 1.12H), 4.02 (q, J=7.0 Hz, 0.88H), 2.77-2.71 (m, 2H), 2.52-2.48 (m, 0.88H), 2.43-2.39 (m, 1.12H), 1.91 (d, J=1.4 Hz, 1.32H), 1.89 (d, J=1.3 Hz, 1.68H), 1.45 (t, J=7.0 Hz, 1.68H), 1.41 (t, J=7.0 Hz, 1.32H).
MS (EI): 298 (M+, 10), 191 (16), 163 (3), 145 (100), 117 (14), 107 (26), 91 (8), 77 (11).
(4-(tert-Butyldimethylsilyloxy)-3-ethoxyphenyl)methyltriphenylphosphonium bromide (1.15 g, 1.89 mmol, 1.0 equiv.) in THF (8 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 1.2 mL, 1.89 mmol, 1.0 equiv.) at 0° C., the red solution was stirred at 65° C. for 1 h. The mixture was re-cooled to 0° C., 3-(3-isopropylphenyl)butanal (541 mg, 2.84 mmol, 1.5 equiv.) in THF (3 mL) was added, and the mixture was stirred at 65° C. for 18 h. After addition of H2O, the aqueous layer was extracted with cyclohexane (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 98:2) to yield a colorless oil which was dissolved in THF (10 mL). n-Bu4NF (1.0 M in THF, 2.3 mL, 2.27 mmol, 1.2 equiv.) was added, and the mixture was stirred at 25° C. for 1 h. After addition of H2O, the aqueous layer was extracted with EtOAc (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 19:1→9:1) to yield 0.33 g (54% over 2 steps) of the title compound as a yellow oil.
1H-NMR (CDCl3, 400 MHz): 7.27-7.21 (m, 1H), 7.08-7.02 (m, 3H), 6.89-6.74 (m, 3H), 6.35-6.28 (m, 1H), 5.98 (ddd, J=15.7, 7.8, 6.6 Hz, 0.6H), 5.65 (s, 0.4H), 5.63 (s, 0.6H), 5.52 (dt, J=11.8, 7.1 Hz, 0.4H), 4.16-4.05 (m, 2H), 2.93-2.80 (m, 2H), 2.64-2.35 (m, 2H), 1.46-1.42 (m, 3H), 1.31-1.24 (m, 9H).
MS (EI): 324 (M+, 6), 177 (36), 147 (11), 131 (100), 117 (5), 103 (23), 91 (10), 77 (6), 43 (12).
Following the general procedure as described in Example 13 the following compounds have been prepared:
Starting from (4-(tert-butyldimethylsilyloxy)-3-ethoxyphenyl)methyltriphenyl-phosphonium bromide (2.14 g, 3.52 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 2.2 mL, 3.52 mmol, 1.0 equiv.) and 2-methylundecanal (0.97 g, 5.28 mmol, 1.5 equiv.), a colorless oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 97:3) which was dissolved in THF. After treatment of that solution with n-Bu4NF (1.0 M in THF, 3.0 mL, 2.97 mmol, 1.2 equiv.), 0.63 g (56% over 2 steps) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 98:2→9:1).
1H-NMR (CDCl3, 400 MHz): 6.88-6.77 (m, 3H), 6.28-6.22 (m, 1H), 5.91 (dd, J=15.8, 8.0 Hz, 0.7H), 5.61 (s, 0.3H), 5.61 (s, 0.7H), 5.33 (dd, J=11.6, 10.4 Hz, 0.3H), 4.16-4.08 (m, 2H), 2.77-2.69 (m, 0.3H), 2.28-2.19 (m, 0.7H), 1.47-1.43 (m, 3H), 1.36-1.23 (m, 16H), 1.06 (d, J=6.6 Hz, 2.1H), 1.03 (d, J=6.8 Hz, 0.9H), 0.90-0.86 (m, 3H).
MS (EI): 318 (M+, 22), 303 (2), 191 (69), 164 (6), 145 (100), 117 (18), 91 (9), 77 (5), 55 (12), 43 (21).
Starting from (4-(tert-butyldimethylsilyloxy)-3-ethoxyphenyl)methyltriphenyl-phosphonium bromide (2.30 g, 3.79 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 2.4 mL, 3.79 mmol, 1.0 equiv.) and 2-(2-(4-methylcyclohex-3-enyl)propyl)cyclo-pentanone (1.17 g, 5.30 mmol, 1.4 equiv.), a light yellow oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 99:1) which was dissolved in THF. After treatment of that solution with n-Bu4NF (1.0 M in THF, 2.5 mL, 2.46 mmol, 1.2 equiv.), 0.19 g (14% over 2 steps) of the title compound as a viscous yellow oil was obtained after purification by flash chromatography on SiO2 (hexanes/EtOAc 97:3→9:1).
1H-NMR (CDCl3, 400 MHz): 6.89-6.79 (m, 3H), 6.22-6.15 (m, 1H), 5.58 (s, 1H), 5.39-5.33 (m, 1H), 4.15-4.06 (m, 2H), 2.60-2.54 (m, 2H), 2.00-1.14 (m, 21H), 0.93-0.86 (m, 3H).
MS (EI): 354 (M+, 100), 257 (25), 229 (10), 217 (35), 171 (45), 151 (24), 121 (18).
A solution of 1-(2-naphthyl)ethyltriphenylphosphonium bromide (2.30 g, 4.62 mmol, 1.0 equiv.) in THF (16 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 2.9 mL, 4.62 mmol, 1.0 equiv.) at 0° C., the red-brown suspension was stirred at 0° C. for 15 min. 3-(3-Isopropylphenyl)butanal (1.32 g, 6.94 mmol, 1.5 equiv.) in THF (2 mL) was added, and the mixture was stirred at 0° C.→70° C. for 18 h. After addition of H2O, the aqueous layer was extracted with hexanes (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3) to yield 0.57 g (38%) of the title compound as a colorless viscous oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, watery, powdery.
1H-NMR (CDCl3, 400 MHz): 7.84-7.73 (m, 4H), 7.54-7.40 (m, 3H), 7.28-7.18 (m, 1H), 7.13-6.93 (m, 3H), 5.94-5.90 (m, 0.75H), 5.54-5.50 (m, 0.25H), 2.97-2.73 (m, 2H), 2.57-2.52 (m, 1.5H), 2.36-2.23 (m, 0.5H), 2.09-2.07 (m, 3H), 1.38-1.20 (m, 9H).
MS (EI): 328 (M+, 6), 181 (100), 165 (27), 147 (19), 115 (5), 105 (9), 91 (6), 77 (2), 43 (10).
Following the general procedure as described in Example 15 the following compounds have been prepared:
Starting from (1-(2-naphthyl)ethyltriphenylphosphonium bromide (2.40 g, 4.83 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.0 mL, 4.83 mmol, 1.0 equiv.) and (2E,6Z)-Nona-2,6-dienal (1.00 g, 7.24 mmol, 1.5 equiv.), and after stirring the mixture at 25° C. for 3 h, 0.90 g (67%) of the title compound as a a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, green, watery, fatty, dark tea, mimosa.
1H-NMR (CDCl3, 400 MHz): 7.85-7.78 (m, 4H), 7.70-7.64 (m, 1H), 7.50-7.39 (m, 2H), 6.63-6.51 (m, 1.6H), 6.22-6.15 (m, 0.4H), 5.93-5.86 (m, 0.8H), 5.76-5.69 (m, 0.2H), 5.50-5.26 (m, 2H), 2.31-2.20 (m, 6H), 2.13-1.96 (m, 3H), 1.00 (t, J=7.6 Hz, 2.3H), 0.93 (t, J=7.5 Hz, 0.7H).
MS (EI): 276 (M+, 25), 261 (1), 207 (100), 192 (57), 179 (45), 165 (40), 152 (13), 141 (11), 128 (8), 115 (9), 77 (9), 41 (18).
Starting from (1-(2-naphthyl)ethyltriphenylphosphonium bromide (4.50 g, 9.05 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 5.7 mL, 9.05 mmol, 1.0 equiv.) and (E)-dec-4-enal (2.09 g, 13.6 mmol, 1.5 equiv.), and after stirring the mixture at 25° C. for 3 h, 1.16 g (44%) of the title compound as a light yellow oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, orange, flowery, powdery, aldehydic, sharp green.
1H-NMR (CDCl3, 400 MHz): 7.85-7.77 (m, 4H), 7.64-7.58 (m, 1H), 7.50-7.41 (m, 2H), 5.99-5.95 (m, 0.6H), 5.58-5.31 (m, 2.4H), 2.37-1.95 (m, 9H), 1.42-1.21 (m, 6H), 0.91-0.87 (m, 3H).
MS (EI): 292 (M+, 5), 181 (100), 165 (28), 153 (5), 141 (5), 128 (2), 115 (2), 41 (5).
Starting from (1-(2-naphthyl)ethyltriphenylphosphonium bromide (6.40 g, 12.9 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 8.0 mL, 12.9 mmol, 1.0 equiv.) and 2-methylundecanal (3.56 g, 19.3 mmol, 1.5 equiv.), and after stirring the mixture at 25° C. for 3 h, 0.94 g (23%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, orange flower, soft, aldehydic.
1H-NMR (CDCl3, 400 MHz): 7.84-7.77 (m, 4H), 7.64-7.60 (m, 1H), 7.50-7.40 (m, 2H), 5.73 (dd, J=9.5, 1.4 Hz, 0.75H), 5.29 (dd, J=10.2, 1.4 Hz, 0.25H), 2.65-2.55 (m, 0.75H), 2.27-2.22 (m, 0.25H), 2.16 (d, J=1.3 Hz, 2.25H), 2.10 (d, J=1.5 Hz, 0.75H), 1.41-1.20 (m, 16H), 1.07 (d, J=6.6 Hz, 2.25H), 0.95 (d, J=6.6 Hz, 0.75H), 0.91-0.88 (m, 3H).
MS (EI): 322 (M+, 13), 307 (3), 195 (100), 179 (14), 165 (24), 155 (13), 141 (9), 128 (4), 115 (2), 43 (8).
Starting from (1-(2-naphthyl)ethyltriphenylphosphonium bromide (2.80 g, 5.63 mmol, 1.0 equiv.), n-BuLi (1.6 M in hexanes, 3.5 mL, 5.63 mmol, 1.0 equiv.) and 3,5,5-trimethylhexanal (1.20 g, 8.44 mmol, 1.5 equiv.), and after stirring the mixture at 25° C. for 3 h, 0.73 g (46%) of the title compound as a colorless oil was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 997:3).
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): floral, orange, flowery, slightly sweet, medicinal.
1H-NMR (CDCl3, 400 MHz): 7.84-7.78 (m, 4H), 7.63-7.60 (m, 1H), 7.48-7.41 (m, 2H), 6.01-5.96 (m, 0.75H), 5.60-5.55 (m, 0.25H), 2.30-1.86 (m, 5H), 1.78-1.55 (m, 1H), 1.40-1.35 (m, 1H), 1.18-1.13 (m, 1H), 1.03 (d, J=6.6 Hz, 2.25H), 0.95 (s, 6.7H), 0.89 (d, J=6.6 Hz, 0.75H), 0.85 (s, 2.3H).
MS (EI): 280 (M+, 13), 265 (1), 181 (100), 165 (26), 155 (8), 141 (3), 128 (3), 115 (3), 57 (14), 41 (8).
Starting from (1-(2-naphthyl)ethyltriphenylphosphonium bromide (49.7 g, 100 mmol, 1.0 equiv.) in THF (400 mL), KtBuO (110 mL, 110 mmol, 1.1 equiv., 1M in THF) and (E)-undec-9-enal (16.8 g, 120 mmol, 1.2 equiv.) in THF (100 mL), 16.6 g (53%) of the title compound was obtained after purification by flash chromatography on SiO2 (hexane) as a light yellow oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): soft aldehydic metallic, floral.
1H-NMR (CDCl3, 400 MHz): 7.86-7.79 (m, 4H), 7.66-7.61 (m, 1H), 7.50-7.42 (m, 2H), 5.99 (ddd, J=1.0, 7.2, 7.2 Hz, 0.7H), 5.58 (ddd, J=1.2, 7.4, 7.4 Hz, 0.3H), 5.51-5.38 (m, 2H), 2.32-2.26 (m, 2H), 2.18-2.15 (m, 3H), 2.11-1.93 (m, 3H), 1.69-1.61 (m, 2H), 1.56-1.25 (m, 10H).
MS (EI): 306 (M+, 21), 291 (1), 181 (100), 168 (59), 155 (30), 141 (20), 128 (10), 115 (5), 55 (17), 41 (12).
4-(4-(3-Isopropylphenyl)pent-1-enyl)-1,2-dimethoxybenzene
A solution of (3,4-dimethoxyphenyl)methyltriphenylphosphonium bromide (4.93 g, 10.0 mmol, 1.0 equiv.) in THF (10 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 6.3 mL, 10.0 mmol, 1.0 equiv.) at 0° C., the red suspension was stirred at 0° C. for 20 min. 3-(3-Isopropylphenyl)butanal (2.09 g, 11.0 mmol, 1.1 equiv.) in THF (11 mL) was added, and the mixture was stirred at 0° C.→25° C. for 16 h. After addition of H2O at 25° C., the aqueous layer was extracted with hexanes (2×), the combined organic phases were dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (hexanes/EtOAc 99:1→4:1) to yield 2.67 g (82%) of the title compound as a colorless oil.
1H-NMR (CDCl3, 400 MHz): 7.30-7.24 (m, 1H), 7.12-7.05 (m, 3H), 6.91-6.81 (m, 3H), 6.42-6.34 (m, 1H), 6.10-6.02 (m, 0.5H), 5.59 (td, J=11.6, 7.1 Hz, 0.5H), 3.91-3.89 (m, 6H), 2.97-2.86 (m, 2H), 2.68 (dt, J=7.2, 1.8 Hz, 1H), 2.60-2.53 (m, 0.5H), 2.48-2.41 (m, 0.5H), 1.36-1.27 (m, 9H).
MS (EI): 324 (M+, 6), 177 (100), 147 (9), 131 (7), 115 (5), 103 (5), 91 (8), 77 (3), 43 (7).
A solution of (benzo[d][1,3]dioxol-5-ylmethyl)triphenylphosphonium bromide (4.77 g, 10.0 mmol, 1.0 equiv.) in THF (20 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 6.3 mL, 10.0 mmol, 1.0 equiv.) at 0° C., the dark red suspension was stirred at 0° C. for 10 min. 3-(3-Isopropylphenyl)butanal (1.90 g, 10.0 mmol, 1.0 equiv.) in THF (10 mL) was added, and the mixture was stirred at 0° C.→25° C. for 16 h. After addition of H2O at 25° C., the aqueous layer was extracted with hexanes and MTBE, the combined organic phases were dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (hexanes/EtOAc 4:1) to yield 2.35 g (75%) of the title compound as a yellow oil.
1H-NMR (CDCl3, 400 MHz): 7.29-7.24 (m, 1H), 7.11-7.04 (m, 3H), 6.88 (br. s, 0.6H), 6.81-6.72 (m, 2.4H), 6.36-6.30 (m, 1H), 6.04-5.98 (m, 0.6H), 5.97 (s, 0.8H), 5.94 (s, 1.2H), 5.55 (td, J=11.7, 7.0 Hz, 0.4H), 2.96-2.84 (m, 2H), 2.65-2.38 (m, 2H), 1.34-1.27 (m, 9H).
MS (EI): 308 (M+, 13), 161 (88), 147 (28), 131 (100), 117 (6), 103 (45), 91 (11), 77 (16), 43 (16).
Potassium t-pentylat (1.7 M in toluene, 6.5 mL, 11.0 mmol, 1.1 equiv.) was added to a solution of (benzo[d][1,3]dioxol-5-ylmethyl)triphenylphosphonium bromide (4.77 g, 10.0 mmol, 1.0 equiv.) in THF (20 mL) at 25° C. After the dark red suspension was stirred at 25° C. for 15 min, 3-(4-methoxyphenyl)-2-methylpropanal (1.78 g, 10.0 mmol, 1.0 equiv.) in THF (10 mL) was added, and the mixture was stirred at 70° C. for 1.5 h. After addition of 20% aq. AcOH-solution (10 mL) at 25° C., the aqueous layer was extracted with MTBE, the combined organic phases were dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (hexanes/EtOAc 19:1) to yield 2.20 g (74%) of the title compound as a yellow oil.
1H-NMR (CDCl3, 400 MHz): 7.13-7.05 (m, 2H), 6.91-6.60 (m, 5H), 6.30-6.23 (m, 1H), 6.03 (dd, J=15.8, 7.0 Hz, 0.8H), 5.95 (s, 0.4H), 5.94 (s, 1.6H), 5.43 (dd, J=11.6, 10.4 Hz, 0.2H), 3.81 (s, 2.3H), 3.80 (s, 0.7H), 3.05-2.97 (m, 0.2H), 2.78-2.53 (m, 2.8H), 1.09 (d, J=6.3 Hz,, 2.3H), 1.05 (d, J=6.6 Hz, 0.7H).
MS (EI): 296 (M+, 9), 175 (90), 145 (100), 121 (23), 115 (51), 91 (14), 77 (11).
Potassium t-butylat (1 Min THF, 11 mL, 11.0 mmol, 1.1 equiv.) was added to a solution of (benzo[d][1,3]dioxol-5-ylmethyl)triphenylphosphonium bromide (4.77 g, 10.0 mmol, 1.0 equiv.) in THF (20 mL) at 25° C. After the dark red suspension was stirred at 25° C. for 10 min, 3-(4-tert-butylphenyl)-2-methylpropanal (2.04 g, 10.0 mmol, 1.0 equiv.) in THF (10 mL) was added, and the mixture was stirred at 70° C. for 1.5 h. After addition of 20% aq. AcOH-solution (10 mL) at 25° C., the aqueous layer was extracted with hexanes, the combined organic phases were dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (hexanes/EtOAc 19:1) to yield 2.83 g (88%) of the title compound as a yellow oil.
1H-NMR (CDCl3, 400 MHz): 7.29-7.24 (m, 2H), 7.09-7.02 (m, 2H), 6.86-6.48 (m, 3H), 6.24-6.20 (m, 1H), 6.01 (dd, J=15.9, 7.1 Hz, 0.8H), 5.89 (s, 2H), 5.39 (dd, J=11.5, 10.4 Hz, 0.2H), 2.99-2.91 (m, 0.2H), 2.75-2.49 (m, 2.8H), 1.30-1.26 (m, 9H), 1.04 (d, J=6.4 Hz, 2.3H), 1.00 (d, J=6.6 Hz, 0.7H).
MS (EI): 322 (M+, 5), 175 (100), 145 (97), 127 (6), 117 (34), 91 (13).
A solution of (4-methoxyphenyl)methyltriphenylphosphonium bromide (2.40 g, 5.18 mmol, 1.0 equiv.) in THF (10 mL), was cooled to 0° C. After adding n-BuLi (1.6 M in hexanes, 3.2 mL, 5.18 mmol, 1.0 equiv.) at 0° C., the red suspension was stirred at 0° C. for 15 min. 3-(4-tert-Butylphenyl)-2-methylpropanal (1.59 g, 7.77 mmol, 1.5 equiv.) in THF (4 mL) was added, and the mixture was stirred at 0° C.→25° C. for 12 h. After addition of H2O at 25° C., the aqueous layer was extracted with hexanes, the combined organic phases were dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 995:5→99:1) to yield 1.33 g (83%) of the title compound as a colorless oil.
1H NMR (CDCl3, 400 MHz): 7.32-7.28 (m, 3H), 7.14-7.03 (m, 3H), 6.87-6.81 (m, 2H), 6.32-6.28 (m, 1H), 6.09 (dd, J=15.9, 7.1 Hz, 0.6H), 5.45 (dd, J=11.4, 10.4 Hz, 0.4H), 3.82 (s, 3H), 3.06-2.98 (m, 0.4H), 2.80-2.54 (m, 2.6H), 1.33 (s, 5.4H), 1.32 (s, 3.6H), 1.09 (d, J=6.6 Hz, 1.8H), 1.04 (d, J=6.6 Hz, 1.2H).
MS (EI): 308 (M+, 2), 293 (1), 161 (100), 146 (5), 131 (5), 117 (8), 91 (8).
Following the general procedure as described in Example 19, starting from cis-3-hexenyltriphenylphosphonium iodide (6.50 g, 13.8 mmol, 1.0 equiv.), n-BuLi (9.5 mL, 15.1 mmol, 1.0 equiv., 1.6 M in hexane) and 4-methoxybenzaldehyde (2.25 g, 16.5 mmol, 1.2 equiv.), 2.60 g (93%) of the title compound (ratio (1E)-isomer: (1Z)-isomer=9:1) was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 99:1) as a colorless oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): green floral natural, mimosa linden blossom.
1H NMR (CDCl3, 400 MHz): 7.31-7.23 (m, 2H), 6.90-6.83 (m, 2H), 6.41-6.32 (m, 1H), 6.07 (dd, J=15.9, 6.6 Hz, 0.9H), 5.59-5.40 (m, 2.1H), 3.81 (s, 3H), 3.08-2.87 (m, 2H), 2.15-2.03 (m, 2H), 1.01 (t, J=7.6 Hz, 2.7H), 0.98 (t, J=7.6 Hz, 0.3H).
MS (EI): 202 (M+, 33), 173 (56), 158 (33), 134 (100), 128 (17), 121 (40), 115 (29), 103 (11), 91 (26), 77 (17), 65 (10), 51 (8), 39 (10).
Potassium t-butylat (17.1 mL, 17.1 mmol, 1.0 equiv., 1M in THF) was added to a solution of (4-methoxyphenyl)methyltriphenylphosphonium bromide (7.90 g, 17.1 mmol, 1.0 equiv.) in THF (17 mL) at 25° C. After the dark red suspension was stirred at 25° C. for 10 min, 3-(3-isopropylphenyl)butanal (3.24 g, 17.1 mmol, 1.0 equiv.) in THF (8.5 mL) was added, and the mixture was stirred at 25° C. 12 h. After addition of 20% aq. AcOH-solution at 25° C., the aqueous layer was extracted with hexane. The combined organic phases were washed with MeOH/H2O (4:1; 2-3x), dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 995:5→99:1) to yield 4.03 g (80%) of the title compound as a light yellow oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): green, floral, florhydral-like.
1H-NMR (CDCl3, 400 MHz): 7.27-7.18 (m, 3H), 7.09-7.03 (m, 3H), 6.89-6.82 (m, 2H), 6.38-6.32 (m, 1H), 6.02 (ddd, J=15.8, 8.0, 6.6 Hz, 0.55H), 5.54 (dt, J=11.6, 7.1 Hz, 0.45H), 3.83 (s, 1.4H), 3.81 (s, 1.6H), 2.94-2.81 (m, 2H), 2.64-2.37 (m, 2H), 1.32-1.25 (m, 9H).
MS (EI): 294 (M+, 4), 147 (100), 131 (4), 115 (10), 105 (5), 91 (13), 77 (3), 43 (6).
Following the general procedure as described in Example 21 the following compounds have been prepared:
Starting from (4-methoxyphenyl)methyltriphenylphosphonium bromide (14.0 g, 30.2 mmol, 1.0 equiv.), KtBuO (34 mL, 34.0 mmol, 1.1 equiv., 1M in THF) and (E)-dec-4-enal (5.59 g, 36.3 mmol, 1.2 equiv.), 5.59 g (72%) of the title compound was obtained after purification by flash chromatography on SiO2 (cyclohexane/EtOAc 99:1) as a light yellow oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): green, fatty, floral, (E)-dec-4-enal-like.
1H-NMR (CDCl3, 400 MHz): 7.30-7.22 (m, 2H), 6.90-6.83 (m, 2H), 6.38-6.33 (m, 1H), 6.10 (dt, J=15.8, 6.7 Hz, 0.6H), 5.58 (dt, J=11.6, 7.1 Hz, 0.4H), 5.47-5.41 (m, 2H), 3.82 (s, 1.2H), 3.81 (s, 1.8H), 2.40 (dq, J=7.3, 1.8 Hz, 0.8H), 2.29-2.21 (m, 1.2H), 2.18-2.12 (m, 2H), 2.02-1.96 (m, 2H), 1.40-1.25 (m, 6H), 0.91-0.88 (m, 3H).
MS (EI): 258 (M+, 4), 147 (100), 132 (4), 115 (10), 103 (5), 91 (13), 78 (3), 41 (5).
Starting from (4-methoxyphenyl)methyltriphenylphosphonium bromide (6.00 g, 13.0 mmol, 1.0 equiv.), KtBuO (14 mL, 14.2 mmol, 1.1 equiv., 1M in THF) and 2-methylundecanal (2.86 g, 15.5 mmol, 1.2 equiv.), 1.98 g (53%) of the title compound was obtained after purification by flash chromatography on SiO2 (hexane/EtOAc 99:1) as a colorless oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): ciste, incense, aldehydic (2-methylundecanal-like).
1H-NMR (CDCl3, 400 MHz): 7.32-7.29 (m, 2H), 6.89-6.83 (m, 2H), 6.32-6.27 (m, 1H), 5.97 (dd, J=15.9, 7.8 Hz, 0.8H), 5.36 (dd, J=11.4, 10.4 Hz, 0.2H), 3.83 (s, 0.6H), 3.82 (s, 2.4H), 2.78-2.71 (m, 0.2H), 2.32-2.21 (m, 0.8H), 1.45-1.25 (m, 16H), 1.08 (d, J=6.6 Hz, 2.4H), 1.05 (d, J=6.8 Hz, 0.6H), 0.90 (t, J=6.8 Hz, 3H).
MS (EI): 288 (M+, 9), 273 (1), 161 (100), 146 (5), 134 (6), 121 (14), 115 (4), 91 (6), 43 (5).
Potassium f-butylat (45 mL, 45 mmol, 1.0 equiv., 1M in THF) and 4-[4-(tert-butyldimethylsilyloxy)phenyl]butan-2-one (12.5 g, 45 mmol, 1.0 equiv.) in THF (23 mL) were added simultaneously to a solution of (m-tolyl)methyltriphenylphosphonium bromide (20.1 g, 45 mmol, 1.0 equiv.) in THF (45 mL) at 70° C. The mixture was stirred at 70° C. for 16 h. After addition of 20% aq. AcOH-solution at 25° C., the aqueous layer was extracted with hexane. The combined organic phases were washed with MeOH/H2O (4:1; 2-3×), dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (cyclohexane/EtOAc 99:1) to yield tert-butyl{4-[4-(4-methoxyphenyl)-3-methylbut-3-en-1-yl]phenoxy}-dimethylsilane as a light yellow oil. This compound was dissolved in THF (32 mL), n-Bu4NF (35 mL, 35 mmol, 0.8 equiv., 1.0 M in THF) was added, and the mixture was stirred at 25° C. for 1 h. After addition of H2O, the aqueous layer was extracted with MTBE (2×), the combined organic phases were washed with brine, dried (MgSO4), filtered and the filtrate was concentrated. The residue was purified by flash chromatography on SiO2 (hexane/EtOAc 9:1→4:1) to yield 7.40 g (65% over 2 steps) of the title compound as a light yellow oil.
Odor description (dry-down of a 10% DPG solution after 24 hours on a smelling strip): raspberry, fruity, floral.
1H-NMR (CDCl3, 400 MHz): 7.24-7.18 (m, 1H), 7.12-6.94 (m, 5H), 6.80-6.74 (m, 2H), 6.31 (s, 0.4H), 6.24 (s, 0.6H), 4.67 (s, 0.6H), 4.66 (s, 0.4H), 2.80-2.74 (m, 2H), 2.52-2.48 (m, 0.8H), 2.46-2.42 (m, 1.2H), 2.36 (s, 1.8H), 2.34 (s, 1.2H), 1.94 (d, J=1.5 Hz, 1.2H), 1.91 (d, J=1.3 Hz, 1.8H).
MS (EI): 252 (M+, 15), 145 (57), 129 (14), 115 (13), 107 (100), 91 (6), 77 (14).
The stability of the compounds has been measured in standard consumer product bases (LD=liquid detergent base, FS=fabric conditioner, SH=shampoo). Therefore, the consumer product containing the compound of formula (I) were stored at room temperature for one day and then at 37° C. for up to three months. Samples have been taken after one day, one month and three months respectively. They have been diluted with acetone, and analyzed for the amount of unchanged compound (i.e. the amount of compound of formula (I)) left in the sample with HPLC, indicated as mol % recovery. The results are given in Table 1 below.
To a non fragranced heavy duty liquid detergent base (pH 8.4) was added 0.1% wt/wt of either, a compound of formula (I) or the corresponding free fragrant aldehyde/ketone and, when olfactively pure available, together with the corresponding carbonyl compound. A sample of this base (34 g) was used to wash a load of 5 cotton terry towels (ca. 200 g dry weight each, about 1 kg total load) in a standard frontloading European washing machine. The wash cycle was carried out at 40° C., followed by two cold rinse cycles and spinning at 1000 rpm. The washed towels were assessed blind by a panel of experienced evaluators for fragrance intensity at TO (wet if not otherwise stated) and after 24 h line dry at room temperature. The intensity was indicated according to the following scale: 0 (odorless), 1 (very weak), 2 (weak), 3 (medium), 4 (strong), 5 (very strong). The results are given in Table 2 below.
As can be seen from the results given in the Table 2 above, the compounds of formula (I) showed higher odor scores on dry clothes compared to the free aldehydes/ketones, thereby demonstrating a desired controlled release effect. For some of the dry clothes additional assessment was carried out after 5 days and the towels washed with the compounds of the present invention still showed perceivable odors whereas those washed with the free aldehydes/ketones were in general odorless.
To a non fragranced fabric conditioner, containing 12% of the ester-quat type cationic surfactant Rewoquat WE18, was added 2% wt/wt of either, a compound of formula (I) or the corresponding free fragrant aldehyde/ketone as a 10% solution in dipropylene glycol (DPG).
A mixed load of fabric containing 4 cotton terry towels was rinsed with the fabric conditioner preparations described above (35 g). The washed towels were assessed wet (T0) and after 24 hours line drying at room temperature for fragrance intensity by a panel experienced evaluators. The coded towels were assessed blind. The intensity was indicated according to the following scale: 0 (odorless), 2 (very weak), 4 (weak), 6 (medium), 8 (strong), 10 (very strong). The results are given in Table 3 below.
The compounds of formula (I) showed higher odour scores on dry clothes compared to the free aldehydes/ketones, thereby demonstrating a desired controlled release effect. Furthermore, several towels were reassessed after 7 days and a further increase in fragrance intensity was noted for some of them.
To a non fragranced bleach powder detergent base was added 0.1% wt/wt of either, a compound of formula (I) or the corresponding free fragrant aldehyde/ketone, as a 10% solution in DPG. The samples were stored at 37° C. for one month.
A mixed load of fabric (total 2.5 kg) containing 4 cotton terry towels for evaluation was washed in a standard frontloading washing machine using the above prepared powder detergent base (90 g). The wash cycle was carried out at 40° C., followed by two cold rinse cycles and spinning. The washed towels were assessed by a panel of 5 experienced evaluators for fragrance intensity after tumble drying and after 24 h line drying at room temperature. The intensity was indicated according to the following scale: 0 (odorless) to 10 (very strong). The coded towels were assessed blind. The results are given in Table 4 below.
Table 4: Fragrance intensity of the free fragrant and a precursor releasing said fragrant
The compounds of the present invention showed higher odour scores on dry clothes after 24 hours and one week respectively compared to the free aldehyde/ketone, thereby demonstrating a desired controlled release effect. Almost all the performance of the raw materials was lost on storage, whereas the compounds of formula (I) largely maintained its level of performance.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1021864.2 | Dec 2010 | GB | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP11/74003 | 12/23/2011 | WO | 00 | 6/20/2013 |
