WO2019166314A1 - Précurseurs thioéthers pour cétones et aldéhydes odorants - Google Patents

Précurseurs thioéthers pour cétones et aldéhydes odorants Download PDF

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Publication number
WO2019166314A1
WO2019166314A1 PCT/EP2019/054294 EP2019054294W WO2019166314A1 WO 2019166314 A1 WO2019166314 A1 WO 2019166314A1 EP 2019054294 W EP2019054294 W EP 2019054294W WO 2019166314 A1 WO2019166314 A1 WO 2019166314A1
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Prior art keywords
thio
methyl
butanal
compound
formula
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Felix Flachsmann
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Givaudan SA
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Givaudan SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3427—Organic compounds containing sulfur containing thiol, mercapto or sulfide groups, e.g. thioethers or mercaptales
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/507—Compounds releasing perfumes by thermal or chemical activation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/50—Spiro compounds

Definitions

  • the present invention relates to a use of a compound of formula (I), to a composition of matter comprising a compound of formula (I), to afragrance ingredient comprising a compound of formula (I), to a compound of formula (I) and to a method for producing a compound of formula (I) according to the independent claims.
  • Fruity, exotic, blackcurrant or passionfruit notes are popular in perfumery and constitute attractive alternatives to hesperidic-citrus, lavender or aldehydic scents.
  • fragrance ingredients include Corps Cassis (4-(methylthio)-4-methyl-2-pentanone), Oxane ((2R, 4S)-2-methyl-4-propyl-1 ,3-oxathiane) and Cassyrane (5-tert-butyl-2-methyl-5- propyl-2FI-furan).
  • blackcurrant notes are top notes that consist of small molecules with a relatively low molecular weight that evaporate quickly. Since they are perceived immediately after application of a perfume, top notes are important for the initial impression thereof.
  • top notes also have a relatively low persistence and are often perceived only over a short period of time.
  • High volatility and poor substantivity can be a problem when a prolonged effect of a fragrance is required, both in fine and functional perfumery.
  • laundry applications require continuous effectiveness of a perfume over a certain period of time after washing and drying of the textiles.
  • a prolonged effectiveness of perfumes can be required.
  • R T and R 4 together with the carbon atoms to which they and R 2 are attached form a 5,
  • R 6 or 7 membered ring preferably a hydrocarbon ring, a lactone or a cyclic ether
  • R 2 is H or C 1-4 -alkyl
  • R 3 is H or C 1-4 -alkyl
  • R T and R 2 together with the carbon atoms to which they are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether;
  • R 3 is selected from the group consisting of H, methyl and ethyl; and
  • R 4 is methyl or ethyl; or
  • R 2 and R 4 together with the carbon atoms to which they are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether; is H or C T _ 3 - alkyl ; and R 3 is H or C ⁇ -alkyl.
  • R 5 is FI or a residue comprising 1 to 20 carbon atoms
  • R 6 is a residue comprising 3 to 20 carbon atoms
  • R 5 and R 6 together with the carbon atom to which they are attached form a 5, 6 or 7 membered ring preferably a hydrocarbon ring, a lactone or a cyclic ether.
  • b-Thiocarbonyl compounds are known in the prior art as precursors for the generation of fragrance molecules, as for instance described in WO 2003/049666 A2.
  • y-cleavage only cleavage of the bond between the sulfur atom and the carbon atom in b-position to the carbonyl group (herein referred to as“y-cleavage”) has been reported in the literature. This reaction pathway generally leads to the liberation of a corresponding a,b-unsaturated carbonyl compound (not shown here).
  • d-cleavage cleavage of the bond between the sulfur atom and the carbon atom in d-position to the carbonyl group
  • Another aspect of the present invention relates to the discovery that with compounds of formula (I) also carbonyl compounds of formula (III) are generated.
  • This allows for use of a compound of formula (I) as a precursor for generating a compound of formula (III), in particular an aldehyde or a ketone. Since many perfume ingredients comprising a carbonyl group are known in the prior art, depending on the structure of residues R 5 and R 6 , the odor properties of the compound of formula (III) can be adapted according to a specific application.
  • the compound of formula (I) can therefore also be used as a precursor for a carbonyl compound of formula (III).
  • the compound of formula (I) can also be used as a precursor for compounds of formulas (II) and (III).
  • a“bifragrant precursor” such a precursor is referred to as a“bifragrant precursor”.
  • the structure of residues R ⁇ to R 6 plays an important role with respect to the kinetics for the release of the compounds of formula (II) and/or formula (III).
  • the compound of formula (I) may in addition to d-cleavage also undergo y-cleavage.
  • By careful choice of the residues R ⁇ to R 6 it is possible to tune the fragrance release properties of a compound of formula (I).
  • the person skilled in the art is familiar with the conditions under which fragrance precursors are generally used.
  • a compound of formula (I) commonly takes place under ambient air at a temperature of -20 °Cto 100 °C, preferably -10 °Cto 60 °C, even more preferably 0 °Cto 40 °C, in particular at room temperature.
  • Another aspect of the present invention relates to a method for generating a compound of formula (II) and/or a compound of formula (III) by decomposition of a compound of formula (I).
  • the compounds of formula (I), (II) and (III) have the structures as defined herein above.
  • a further aspect of the present invention refers to a composition of matter comprising a compound of formula (I) and a compound of formula (A).
  • FT is H or C ⁇ s-alkyl
  • R 2 is H or C ⁇ s-alkyl
  • R 3 is H or C T -5 - alkyl
  • R 4 is C ⁇ e-alkyl; or R ⁇ and R 4 together with the carbon atoms to which they and R 2 are attached form a 5,
  • R 6 or 7 membered ring preferably a hydrocarbon ring, a lactone or a cyclic ether
  • R 2 is H or C 1-4 -alkyl
  • R 3 is H or C 1-4 -alkyl
  • R-i and R 2 together with the carbon atoms to which they are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether;
  • R 3 is selected from the group consisting of H, methyl and ethyl; and
  • R 4 is methyl or ethyl; or
  • R 2 and R 4 together with the carbon atoms to which they are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether;
  • R ⁇ is H or C T _ 3 - alkyl ; and
  • R 3 is H or C ⁇ -alkyl;
  • R 5 is H or a residue comprising 1 to 20 carbon atoms; and R 6 is a residue comprising 3 to 20 carbon atoms; or
  • R 5 and R 6 together with the carbon atom to which they are attached form a 5, 6 or 7 membered ring preferably a hydrocarbon ring, a lactone or a cyclic ether.
  • a curly bond (of. R 3 in formula (A)) means that the configuration at a given center is undefined.
  • the double bond in formula (A) may thus be either (E) or (Z).
  • R 1: R 2 , R 3 , R 4 , R 5 and R 6 can be the same for both of the compound of formula (I) and the compound of formula (A), or they can be different. Preferably, they are the same.
  • compositions of matter as specified herein above it has been found that the occurrence of thiol off-odors is suppressed when a compound of formula (A) is present. Consequently, beneficial olfactory properties can be achieved.
  • the amount of the compound of formula (A) in relation to the total amount of the compound of formula (I) and the compound of formula (A) is 0.1-3.0 wt.-%, preferably 0.3-1.2 wt.-%, even more preferably 0.6-1.0 wt.-%.
  • the present invention refers to a fragrance ingredient
  • FT is H or C 1-4 -alkyl
  • R 2 is H or C 1-4 -alkyl
  • R 3 is H or C 1-4 -alkyl
  • R 4 is C 1-4 -alkyl
  • R T and R 4 together with the carbon atoms to which they and R 2 are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether;
  • R 2 is H or C 1-4 -alkyl; and
  • R 3 is H or C 1-4 -alkyl; or
  • R-i and R 2 together with the carbon atoms to which they are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether
  • R 3 is selected from the group consisting of H, methyl and ethyl
  • R 4 is methyl or ethyl
  • R 2 and R 4 together with the carbon atoms to which they are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether
  • R ⁇ is H or C T _ 3 - alkyl
  • R 3 is H or C ⁇ -alkyl.
  • R 5 is FI or a residue comprising 1 to 20 carbon atoms
  • R 6 is a residue comprising 6 to 20 carbon atoms
  • R 5 and R 6 together with the carbon atom to which they are attached form a 5, 6 or 7 membered ring, preferably a non-aromatic ring, in particular a hydrocarbon ring, a lactone or a cyclic ether; wherein the total combined number of carbon atoms of R 1: R 2 , R 3 and R 4 is 1 to 4, preferably 1 to 3, if R 5 is FI and R 6 is selected from a group consisting of octyl, undecyl and heptadecyl.
  • the total combined number of carbon atoms of R 1: R 2 , R 3 and R 4 can also be 1 to 6, preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, irrespective of the nature of R 5 and R 6 .
  • R 5 and R 6 can have the following structural features, either alone or in combination:
  • R 5 can be a residue comprising 4 to 18 carbon atoms, preferably 6 to 16 carbon atoms;
  • R 5 can be an alkyl, alkenyl or aromatic residue
  • R 6 can be a residue comprising 7 to 16 carbon atoms, preferably 8 to 14 carbon atoms, even more preferably 9 to 13 carbon atoms;
  • R 6 can be an alkyl, alkenyl or aromatic residue.
  • the alkyl or alkenyl residues can be linear, cyclic or branched.
  • R 5 and/or R 6 can be hydrocarbon residues. However, they can also have one or more heteroatoms, in particular one, two or three oxygen atoms.
  • the oxygen atoms can be part of ether and ester groups.
  • the compound of formula (I) can be selected from the group consisting of 3- (octylthio)butanal, 4-methyl-4-(octylthio)pentan-2-one, 3-(decylthio)butanal, 4- (decylthio)-4-methylpentan-2-one, 4-(dodecylthio)pentan-2-one, 4-(dodecylthio)-4- methylpentan-2-one, 4-(dodecylthio)-3-methylpentan-2-one, 3-(dodecylthio)-3- methylbutanal, 3-(dodecylthio)butanal, 3-(dodecylthio)butanal, 3-(dodecylthio)-3-methylcyclo
  • a further aspect of the present invention refers to a compound of formula (I).
  • R 2 is H or C ⁇ s-alkyl
  • R 3 is H or C ⁇ s-alkyl
  • R 4 is C ⁇ -alkyl
  • R 6 or 7 membered ring preferably a hydrocarbon ring, a lactone or a cyclic ether
  • R 2 is FI or C 1-4 -alkyl
  • R 3 is FI or C 1-4 -alkyl
  • R T and R 2 together with the carbon atoms to which they are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether;
  • R 3 is selected from the group consisting of H, methyl and ethyl; and
  • R 4 is methyl or ethyl; or
  • R 2 and R 4 together with the carbon atoms to which they are attached form a 5, 6 or 7 membered ring, preferably a hydrocarbon ring, a lactone or a cyclic ether; is FI or C T _ 3 - alkyl ; and R 3 is FI or C ⁇ -alkyl;
  • R 5 is H; and R 6 is selected from the group consisting of 4- isobutylphenethyl, 1 -(4-(tert-butyl)phenyl)propan-2-yl, 4-(tert-butyl)phenethyl, (E)- styryl, phenethyl, (E)-hex-3-en-1 -yl, (Z)-pent-2-en-1 -yl, 1 -(4-isopropylphenyl)propan- 2-yl, 4-isobutyl-2-methylphenethyl, 2-(3-isopropylphenyl)propyl, (Z)-oct-5-en-1 -yl, (Z)-dec-8-en-1 -yl, (Z)-non-7-en-1 -yl, (E)-dodec-1 -en-1 -yl, (1 E,5Z)-octa-1 ,5-dien-1-1
  • the above-mentioned compounds have the advantage that they can generate carbonyl compounds of formula (III) with particularly beneficial olfactory properties.
  • the present invention also refers to a fragrance ingredient comprising a compound of formula (I) or a composition of matter comprising a compound of formula (I) and a compound of formula (A) as herein specified.
  • a fragrance oil or a fragrance composition comprising any kind of fragrance ingredient as herein defined.
  • fragrance oil is to be understood as a mixture of fragrance ingredients.
  • a“fragrance composition” is to be understood as a fragrance ingredient or a fragrance oil that has been mixed with a base material.
  • the base material can comprise a diluent, such as diethyl phthalate (DEP), dipropylene glycol (DPG), isopropyl myristate (I PM), triethyl citrate (TEC) or an alcohol, for instance ethanol.
  • DEP diethyl phthalate
  • DPG dipropylene glycol
  • I PM isopropyl myristate
  • TEC triethyl citrate
  • the base material may also comprise an anti-oxidant.
  • a composition of matter comprising a compound of formula (I) and a compound of formula (A), a fragrance ingredient comprising a compound of formula (I), and/or a compound of formula (I) as described herein above may be used in combination with known fragrance ingredients or fragrance oils, such as:
  • 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), EbanolTM ((E)-3-methyl-5-(2, 2,3- trim ethy lcyclopent-3-en- 1 -y I) pent-4-en-2-ol) , eugenol (4- ally I-2- methoxyphenol) , ethyl linalool ((E)-3,7-dimethylnona-1 ,6-dien-3-ol) , farnesol ((2E,6Z)-3,7,11 - trim ethy ldodeca-2,6, 10-trien-1
  • Aldehydes and ketones e.g. anisaldehyde (4-methoxybenzaldehyde) , alpha amyl cinnamic aldehyde (2-benzylideneheptanal) , GeorgywoodTM (1-(1 ,2,8,8- tet ram ethy 1-1 ,2,3,4,5,6,7,8-octahydronaphthalen-2-yl)ethanone) ,
  • Hydroxycitronellal (7-hydroxy-3,7-dimethyloctanal) , Iso E SuperTM (1-(2,3,8,8- tet ram ethy 1-1 ,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) , 3-(4-isobutyl-2- methylphenyl)propanal, maltol, methyl cedryl ketone, methylionone, verbenone, 2,6,10-trimethylundeca-5,9-dienal, 3-(4-ethylphenyl)-2,2- dimethylpropanal, 1 -methyl-4-(4-methylpent-3-en-1 -yl
  • Ether and acetals e.g. Ambrox® (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b- octahydro-1H-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-2H-pyran), and / or Spirambrene® ( 2 ' , 2’ , 3 , 7 , 7- pentamethylspiro[bicyclo[4.1.0] heptane-2,5'-[ 1 ,3]dioxane]) ;
  • Ambrox® (3a,6,6,9a-tetramethyl-2,4,5,5a,7,8,9,9b- octahydro-1H-benzo[e][
  • esters and lactones e.g. benzyl acetate, cedryl acetate ((1 S,6R,8aR)-1 ,4,4,6- tetramethyloctahydro-1 H-5,8a-methanoazulen-6-yl acetate), decalactone (6- pentyltetrahydro-2H-pyran-2-one), Helvetolide® (2-(1 -(3,3- dim ethylcyclohexy I) et hoxy ) -2- m et hy Ipropy I propionate), undecalactone (5- heptyloxolan-2-one), and/or vetiveryl acetate ((4,8-dimethyl-2-propan-2- ylidene-3,3a,4,5,6,8a-hexahydro-1 H-azulen-6-y I) acetate) ;
  • Macrocycles e.g. Ambrettolide ((Z)-oxacycloheptadec-l 0-en-2-one), ethylene brassylate (1 ,4-dioxacycloheptadecane-5,17-dione), and/or Exaltolide® (16- oxacyclohexadecan-1 -one) ;
  • Heterocycles e.g. isobutylquinoline (2-isobutylquinoline) .
  • the present invention also relates to a consumer product comprising a compound of formula (I), a fragrance ingredient, or a composition of matter comprising a compound of formula (I) and a compound of formula (A) as herein specified.
  • a consumer product means an article intended to be used or consumed in the form in which it is sold, and not intended for subsequent commercial manufacture or modification.
  • the concentration of the compound of formula (I) can be 0.1 to 10 wt.-%, preferably 0.2 to 5 wt.-%, even more preferably 0.5 to 3 wt.-% .
  • the consumer product can be a personal care product, a laundry care product or a household care product.
  • Examples of such products include cosmetics, shampoos, shower gels, deodorants, antiperspirants, laundry detergents, rinse conditioners, fabric softeners, detergents for dishwashers, surface cleaners, in particular for hard and soft surfaces and air care products.
  • a consumer product according to the present invention can, in addition to the compound of formula (I), additionally comprise at least one further compound capable to release at last one molecule having beneficial olfactory properties.
  • the present invention also relates to mixtures of precursors.
  • the at least one further compound can also be a compound of formula (I) but chemically different from the first compound.
  • the at least one further compound can also be of different type, as for instance described in EP 0936 211 A2, WO 2007/143873, A1 WO 2012/085287 A1 , WO 2016/091894 A1 , WO 2016/091899 A1 , WO 2016/074695 A1 , WO 2016/074699 A1 , WO 2018/096176 A1 , WO 2008/093272 A2, WO 2008/ 142591 A2, WO 2009/ 118219 A1 , WO 2010/020954 A1 , WO 2010/029462 A1 , WO 2010/066486 A2, WO 2010/094356 A1 , WO
  • composition over time can be modulated in accordance to the needs of a given application.
  • R 1: R 2 , R 3 and R 4 can have the following structures, either alone or in combination:
  • R T can be selected from the group consisting of methyl, ethyl, n-propyl, iso propyl, n-butyl, sec-butyl and tert-butyl;
  • - R 2 can be selected from the group consisting of methyl, ethyl, n-propyl, iso propyl, n-butyl, sec-butyl and tert-butyl;
  • - R 3 can be selected from the group consisting of methyl, ethyl, n-propyl, iso propyl, n-butyl, sec-butyl and tert-butyl;
  • R 4 can be selected from the group consisting of methyl, ethyl, n-propyl, iso propyl, n-butyl, sec-butyl and tert-butyl.
  • - Ri is H and R 4 is H; - Ri is H and R 4 is methyl;
  • R T is methyl and R 4 is H;
  • R T is methyl and R 4 is methyl.
  • R 1 R 2 , R 3 and R 4 is particularly preferred:
  • R T is H; R 2 is H; R 3 is H; and R 4 is methyl
  • the compound of formula (I) can be selected from the group consisting of 3-((3-(4-(tert-butyl)phenyl)propyl)thio)butanal, 3-((2- methylundecyl)thio) but anal, 3-(phenethylthio)butanal, 3-((4-oxobutan-2-yl)thio)hexyl acetate, 3-((1 -phenylethyl)thio)butanal, 3-((1 -(3,3- dim ethylcyclohexy l)et hy I) t hio) butanal, (Z)-3-(hex-3-en-1 -ylthio)butanal, 3-((6- methyloctyl)thio)butanal, (Z) -3- (non- 6- en- 1 -y It hio) butanal, 3-((3-ethoxy-4- hydroxybenzyl)
  • R T is H; R 2 is H; R 3 is methyl; and R 4 is methyl;
  • R T is methyl;
  • R 2 is H;
  • R 3 is H; and
  • R 4 is methyl;
  • R T is methyl; R 2 is H; R 3 is methyl; and R 4 is methyl.
  • the third combination of residues leads to the generation of the fruity, exotic, blackcurrant and passionfruit fragrance note 4-mercapto-4-methyl-2-pentanone when d-cleavage occurs.
  • the compound of formula (I) can be selected from the group consisting of 4-((3-(4-(tert-butyl)phenyl)propyl)thio)-4-methylpentan-2-one, 4- methyl-4-((2-methylundecyl)thio)pentan-2-one, 4- methyl- 4- (phenethy It hio) pent an -2- one, 3-((2-methyl-4-oxopentan-2-yl)thio)hexyl acetate, 4-methyl-4-((1 - phenylethyl)thio)pentan-2-one, 4-((1 - (3,3-dim ethylcyclohexyl)ethyl)thio)-4- methylpentan-2-one, (Z)-4-(hex-3-en-1-ylthio)-4-methylpentan-2-one, 4-methyl-4- ((6-methyloctyl)thio)pentan-2-one
  • bifragrant precursors which on one hand, as discussed herein above, generate 4-mercapto-4-methyl-2-pentanone and, on the other hand, lead to the formation of ketones and aldehydes, which have proven to be useful in perfumery due their beneficial organoleptic properties. With this simultaneous release, a particular impression of freshness can be achieved.
  • a further aspect of the present invention refers to a method for producing a compound of formula (I) by reaction of a compound of formula (A) with a compound of formula (B).
  • the above-mentioned method can comprise the step of forming a mixture of the compound of formula (A) with the compound of formula (B) in a solvent, wherein the solvent is preferably an alcohol or an ether, in particular selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert- butanol, diethyl ether, diisopropyl ether, di-n-butyl ether, methyl tert-butyl ether, tetrahydrofuran and 2-methyl tetrahydrofuran.
  • the solvent is preferably an alcohol or an ether, in particular selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert- butanol, diethyl ether, diisopropyl ether, di
  • reaction of a compound of formula (A) with a compound of formula (B) can also be conducted in the substantial absence of a solvent.
  • the reaction of a compound of formula (A) with a compound of formula (B) can be conducted in the presence of a base, preferably selected from the group consisting of DBU (1 ,8-diazabicyclo(5.4.0)undec-7-ene), trimethylamine, trimethylam ine, N,N- diisopropylethylamine and urotropine.
  • a base preferably selected from the group consisting of DBU (1 ,8-diazabicyclo(5.4.0)undec-7-ene
  • trimethylamine trimethylam ine
  • N,N- diisopropylethylamine urotropine
  • Fh is H
  • a protic solvent preferably an alcohol, in particular selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec- butanol, tert-butanol.
  • the molar ratio of the compound of formula (A) and the compound of formula (B) can be between 5:1 and 1:1, preferably between 2:1 and 1.05: 1. This has the advantage that removal of a large excess of the compound of formula (B) is avoided.
  • the above-mentioned method can further comprise the step of purifying the compound of formula (I) obtained, preferably by distillation, in particular wiped film distillation, or chromatography.
  • Odor 1% wt/vol in EtOH on blotter after 24 h: cassis, mango, passionfruit, juicy, lindenblossom
  • Example 2 The procedure described in Example 1 was repeated with 2-methylundecane-1 -thiol (preparation see B. Hache, Y. Gareau, Tet. Lett.1994, 35 1837), (8.0 g, 39.5 mmol,
  • Odor 1% wt/vol in EtOH on blotter after 24 h: green, tomato leaves, cassis
  • This thiol was prepared by tosylation of the corresponding alcohol, nucleophilic substitution with potassium thioacetate and reduction of the thioester to the free thiol as described in the following: 3-(4-(tert-Butyl)phenyl)propan-1 -ol (32.7 g, 1 70 m mol, 1 equiv.) was dissolved in MTBE (1 00 m L) and tosyl chloride (33.5 g, 1 equiv.) was added. The solution was cooled to 5° C, then pyridine (29.0 g, 2.1 equiv.) was added dropwise over 15 m in. The cooling bath was removed and the solution was heated to 60°C for 6 h under stirring.
  • the solution was diluted with water and extracted with MTBE.
  • the com bined organic layers were washed with 0.5 M HCI, then with water and brine and dried over MgS0 4 .
  • the solvents were removed by rotary evaporation, and the residue was dried at room tem perature at 0.08 mbar.
  • the tosylate a slightly yellow, viscous oil, was dissolved in DMF ( 170 m L) and potassium thioacetate (39.2 g, 2.0 equiv.) was added and the resulting brown suspension was heated to 80° C for 2 h, cooled to room temperature and left stirring for 1 6 h.
  • Example 2 The procedure described in Example 1 was repeated with 3- (4- (tert- butyl)phenyl)propane-1 -thiol (prepared in example 3a) (2.12 g, 10.2 mmol, 1 equiv.), 4-methylpent-3-en-2-one (1.0 g, 1 equiv.) and DBU (1.54 g, 1 equiv.) in ethanol (5 mL).
  • the crude product was purified by FC with hexane/MTBE 19:1 to yield 4-((3-(4- (tert-butyl)phenyl)propyl)thio)-4-methylpentan-2-one as a colorless liquid (2.22 g, 71%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: fruity, cassis
  • Example 5 4-Methyl-4-f phenethylthioloentan-2-one
  • 2-phenylethane-1 -thiol 5.0 g, 36.2 mmol, 1 equiv.
  • 4-methylpent-3-en-2-one 5.5 g, 1 equiv.
  • DBU 7.1 g, 2 equiv.
  • the crude product was purified by FC with hexane/MTBE 96:4 to yield 4-methyl-4-(phenethylthio)pentan-2-one as a colorless liquid (6.33 g, 74%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: bee’s wax, fruity, cassis
  • This thiol was prepared according to the procedure described in example 3a) from 1- (3,3-dimethylcyclo-hexyl)ethanol and used without purification for the subsequent reaction described in Example 6b) below.
  • Example 2 The procedure described in Example 1 was repeated with 1 - (3 ,3- dim et hy Icy cloh exy I) ethane-1 - thiol (6.9 g, 40 mmol, 1 equiv.), 4-methylpent-3-en-2- one (7.86 g, 2 equiv.) and DBU (6.1 g, 1 equiv.) in THF (80 mL).
  • Example 2 The procedure described in Example 1 was repeated with (Z)-non-6-ene-1 -thiol (6.2 g, 39.2 mmol, 1 equiv.), 4-methylpent-3-en-2-one (7.69 g, 2 equiv.) and DBU (5.96 g, 1 equiv.) in THF (80 mL).
  • the crude product was purified by FC with hexane/MTBE 96:4 to yield 4-((1 -(3,3-dimethylcyclohexyl)ethyl) thio)-4-methylpentan-2-one as a colorless liquid (6.12 g, 61%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: green, fruity, cassis
  • Example 2 The procedure described in Example 1 was repeated with (Z)-Hex-3-ene-1 -thiol (2.8 g, 24.1 mmol, 1 equiv.), 4-methylpent-3-en-2-one (4.73 g, 2 equiv.) and DBU (3.67 g, 1 equiv.) in THF (60 mL).
  • the crude product was purified by FC with hexane/MTBE 96:4 to yield (Z)-4-(hex-3-en-1 -ylthio)-4-methylpentan-2-one as a slightly yellow liquid (2.23 g, 43%).
  • Example 9 4-f Dodecylthio)-3-methylpentan-2-one
  • 1 -dodecanethiol 7.0 g, 34.6 mmol, 1 equiv.
  • E -3-methylpent-3-en-2-one
  • DBU 5.27 g, 1 equiv.
  • the crude product was purified by FC with hexane/MTBE 95:5 to yield 4-(dodecylthio)-3-methylpentan-2-one as a colorless liquid (9.4 g, 90%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: fruity, cassis
  • Example 10 3-f Dodecylthiol-3-methylbutanal
  • 1 -dodecanethiol (24.1 g, 119 mmol, 1 equiv.)
  • 3-methylbut-2-enal (10.0 g, 1 equiv.)
  • DBU (18.1 g, 1 equiv.
  • the crude product was purified by FC with hexane/MTBE 95:5 to yield 3-(dodecylthio)-3-methylbutanal as a colorless liquid (7.0 g, 21%).
  • Example 2 The procedure described in Example 1 was repeated with 1 -dodecanethiol (7.7 g, 38.0 mmol, 1 equiv.), 3-methyl-2-cyclohexen-1 -one (5.03 g, 1.2 equiv.) and DBU (5.79 g, 1 equiv.) in THF (60 mL) during 4 days at room temperature.
  • the crude product was purified by FC with hexane to hexane/MTBE 9: 1 to yield 3-(dodecylthio)-3- methylcyclohexan-1 -one as a colorless liquid (3.09 g, 26%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: aldehydic, floral, green, slightly sulfury
  • Example 12 3-iDodecylthio1-3-methylcvclopentan-1 -one
  • 1 -dodecanethiol 8.7 g, 43.0 mmol, 1 equiv.
  • 3-methylcyclopent-2-enone (4.96 g, 1.2 equiv.)
  • DBU 6.54 g, 1 equiv.
  • the crude product was purified by FC with hexane to hexane/MTBE 9: 1 to yield 3-(dodecylthio)-3- methylcyclopentan-1 -one as a colourless liquid (0.68 g, 5%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h
  • Example 2 The procedure described in Example 1 was repeated with 1 -dodecanethiol (4.9 g, 24.2 mmol, 1 equiv.), 5-methylhex-4-en-3-one (5.43 g, 2 equiv.) and DBU (3.69 g, 1 equiv.) in THF (80 mL) during 20 h at room temperature.
  • the crude product was purified by FCwith hexane/MTBE 96:4 to yield 5-(dodecylthio)-5-methylhexan-3-one as a colourless liquid (3.45 g, 46%).
  • Example 2 The procedure described in Example 1 was repeated with 1 -decanethiol (10.0 g, 57.4 mmol, 1 equiv.), 4-methylpent-3-en-2-one (11.26 g, 2 equiv.) and DBU (8.73 g, 1 equiv.) in THF (80 mL) during 24 h at room temperature.
  • the crude product was purified by FCwith hexane/MTBE 95: 5 to yield 4-(decylthio)-4-methylpentan-2-one as a colourless liquid (14.12 g, 90%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: fruity, sulfury, slightly aldehydic.
  • Example 2 The procedure described in Example 1 was repeated with 1 -tetradecanethiol (4.16 g, 18.1 mmol, 1 equiv.), 4-methylpent-3-en-2-one (3.54 g, 2 equiv.) and DBU (2.75 g, 1 equiv.) in THF (50 mL) during 24 h at room temperature.
  • the crude product was purified by FCwith hexane/MTBE 95: 5 to yield 4-methyl-4-(tetradecylthio)pentan-2- one as a colourless liquid (3.21 g, 54%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: fruity, sulfury, slightly aldehydic.
  • Example 2 The procedure described in Example 1 was repeated with 6-methyloctane-1 -thiol (prepared according to Example 3a) from 6-methyl octanol; 8.5 g, 53 mmol, 1 equiv.), 4-methylpent-3-en-2-one (10.4 g, 2 equiv.) and DBU (8.07 g, 1 equiv.) in THF (120 mL).
  • the crude product was purified by FC with hexane/MTBE 96:4 to yield 4-methyl- 4-((6-methyloctyl)thio)pentan-2-one as a clear, colorless liquid (9.3 g, 68%).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: fruity, cassis, slightly aldehydic.
  • Example 3b The procedure described in Example 3b) was repeated with 3-(4-isobutyl-2- methylphenyl)propane-1 -thiol (prepared according to Example 3a) from 3-(4-isobutyl- 2-methylphenyl)propan-1 -ol ⁇ prepared as described in WO 2014/180945 A1 ⁇ ; 5.1 g, 22.9 mmol, 1 equiv.) and (E)-but-2-enal (3.21 g, 2 equiv.).
  • Example 2 The procedure described in Example 1 was repeated with 3-(4-isobutyl-2- methylphenyl)propane-1 -thiol (prepared according to Example 3a) from 3-(4-isobutyl- 2-methylphenyl)propan-1 -ol ⁇ prepared as described in WO 2014/180945 A1 ⁇ ; 5.1 g, 22.9 mmol, 1 equiv.), 4-methylpent-3-en-2-one (4.5 g, 2 equiv.) and DBU (3.49 g, 1 equiv.) in THF (50 mL).
  • Odor 1% wt/vol in EtOH on blotter after 24 h: fruity, cassis, sulfury.
  • a stainless steel tube (length 25 cm , i.d. 0.8 m m) with a Porapak Q filter (of. R. Kaiser,“Meaningful Scents around the World”, Helvetica Chim ica Acta, Zurich 2006, chapter 1 .3.) attached to its tip with shrinking tube and secured with Parafilm , was introduced into the jar through one of the openings, to which it was attached by an air tight Teflon joint.
  • the tube was attached to a peristaltic pump with a thin rubber hose and the other opening of the jar (the air inlet) was equipped with a charcoal filter. An air volume of 2 L was drawn through the filter with a flow of 1 0 m L/m in.
  • Exam ple 21 Release of odoriferous volatiles from 4-((3-(4-(tert-butvhDhenvhDropyh thio1-4-methyloentan-2-one Exam ple 1 was repeated with 4-((3-(4-(tert-butyl)phenyl)propyl)thio)-4-m ethylpentan- 2-one.
  • fragrance accord has been created for an all-purpose cleaner and is to be assessed at 0.3% in the unperfumed product base.
  • the olfactory character imparted to the product by the reference accord is citrus and fresh floral aldehydic, with a watery facette.
  • Three sam ples of liquid detergent samples (34 g each) were prepared by adding 0.2 wt.-% of the following precursors according to the present invention to a non fragranced heavy duty liquid detergent base (pH 8.4) : 4-(decylthio)-4-m ethylpentan- 2-one ( Example 14) , 4-(dodecylthio)-4-methylpentan-2-one ( Exam ple 1 ) and 4- m ethyl-4-(tetradecylthio)pentan-2-one ( Example 15) .
  • the samples were used to wash a load of 5 cotton terry towels (ca.
  • Exam ple 25 Application in liquid detergent 2 a) General As series of experim ents was conducted in order to determ ine whether fragrance ingredients according to the present invention show intensity benefits in fabric detergents.
  • the com pound of Exam ple 1 (4-(dodecylthio)-4-m ethylpentan-2-one) was tested with two fragrances A and B, which had different olfactive profiles. The products were assessed on wet cloth and on 1 day, 3 days and 7 days dried cloth.
  • the mem bers of a sensory analysis panel were selected on a basis of their olfactory sensory acuity and then trained for several months. Their training enabled them to identify individual odor characteristics and score their perceived intensity against given standards in a consistent m anner.
  • the fabrics were washed in European washing m achines (40° C - 1 ,000 spin/m in) with one unit dose per wash load.
  • European washing m achines 40° C - 1 ,000 spin/m in
  • the cloths were placed into 500 m L wide necked glass jars ready for assessment.
  • the cloth was lined-dried and left overnight in a perfum e free room at 25 ° C. Cloths washed with fragrance A were used as the control.
  • the overall perceived intensity was assessed by the trained sensory panel using a 0- 1 00 linear scale. All overall perceived intensities were scaled against a reference sam ple A, for which the overall perceived intensity was set at 35 for wet cloth assessm ent and 1 0 for the dry cloth assessm ents where the reference sam ple was a 1 day dry cloth.
  • the reference sam ple A was presented in the sam e form at as the test sam ples for the wet cloth and dry cloth assessm ent.
  • each sam ple was assessed twice by 20 panellists, thus giving 40 assessm ents per product.
  • each sam ple was assessed twice by 1 4 panellists, thus giving 28 assessm ents per product.
  • fragrance ingredients according to the present invention show intensity benefits in all purpose cleaners (APCs) .
  • APIs all purpose cleaners
  • the compound of Example 1 (4-(dodecylthio)-4-m ethylpentan-2-one) was tested with two fragrances A and B, which had different olfactive profiles.
  • the mem bers of a sensory analysis panel were selected on a basis of their olfactory sensory acuity and then trained for several months. Their training enabled them to identify individual odor characteristics and score their perceived intensity against given standards in a consistent m anner.
  • the testing was carried out in sm all booths ( 1 0 m 3 booths, 21 °C, 50% RFI) specifically designed. The booths were closed during testing, with the doors sealed.
  • the APC products were diluted at 1 .2% in warm water (45°C + /- 2° C) . 60 m L of the diluted product was applied directly to the booth floor. It was evenly spread using a gloved hand, over an area of 65 cm x 65 cm.
  • the system was assessed through a porthole in the door of the booth.
  • the overall perceived intensity was assessed by the trained sensory panel using a 0-100 line scale.
  • the dilution assessment was conducted over four sessions.
  • the 2 hour stage was assessed by 17 panelists, thus giving 34 assessments per product.
  • Fragrance B + 8% precursor or Fragrance A + 5% precursor were not perceived to be significantly different to booths containing Fragrance B + 4% precursor, but were perceived to be significantly stronger than booths containing Fragrance A or Fragrance B. d) Two hour bloom from floor assessm ent
  • Fragrance B + 4% precursor was comparable in terms of strength to Fragrance B at the fresh, 1 hour and 2 hour assessments, but was perceived to be significantly stronger than Fragrance B when assessed 4 hours after application.
  • Fragrance A + 5% precursor and Fragrance B + 8% precursor were comparable in terms of strength when assessed at all time points (0, 1, 2 and 4 hours).

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Abstract

L'invention concerne un composé de formule (I), un ingrédient de parfum comprenant un composé de formule (I), l'utilisation d'un composé de formule (I) et un procédé de production d'un composé de formule (I).
PCT/EP2019/054294 2018-03-02 2019-02-21 Précurseurs thioéthers pour cétones et aldéhydes odorants Ceased WO2019166314A1 (fr)

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WO2020260598A1 (fr) 2019-06-27 2020-12-30 Firmenich Sa Produits de consommation parfumés
GB202404060D0 (en) 2024-03-21 2024-05-08 Givaudan Sa Fragrance compositions exhibiting enhanced intensity
WO2025196224A1 (fr) 2024-03-21 2025-09-25 Givaudan Sa Compositions de parfum présentant une intensité améliorée
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WO2020260598A1 (fr) 2019-06-27 2020-12-30 Firmenich Sa Produits de consommation parfumés
CN111662262A (zh) * 2020-06-29 2020-09-15 怀宁大有医药科技有限公司 6-(4-((2-环己硫基乙基)氨基)苯基)四氢-2h-吡喃-2-酮的合成方法
CN111662262B (zh) * 2020-06-29 2023-04-28 陕西大美化工科技有限公司 6-(4-((2-环己硫基乙基)氨基)苯基)四氢-2h-吡喃-2-酮的合成方法
WO2025190760A3 (fr) * 2024-03-13 2026-02-26 Firmenich Sa Proparfums libérant de l'oxyde de mésityle
GB202404060D0 (en) 2024-03-21 2024-05-08 Givaudan Sa Fragrance compositions exhibiting enhanced intensity
WO2025196224A1 (fr) 2024-03-21 2025-09-25 Givaudan Sa Compositions de parfum présentant une intensité améliorée

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