SELENIDE DERIVATIVES OF FRAGRANCE COMPOUNDS

Abstract

There is provided the use of selenide derivatives of fragrance compounds comprising an α,β-unsaturated aldehyde moiety, an α,β-unsaturated ketone moiety, an α,β-unsaturated ester moiety, an α,β-unsaturated lactone moiety or an α,β-unsaturated carboxylic acid moiety in consumer products. There are further provided methods for the synthesis of selenide derivatives, certain selenide derivatives, consumer products comprising the selenide derivatives and methods of perfuming an article or surface using such derivatives.

Claims

1. (canceled)

2. A consumer product comprising a selenide derivative of a fragrance compound comprising an α,β-unsaturated aldehyde moiety, an α,β -unsaturated ketone moiety, an α,β -unsaturated ester moiety, an α,β -unsaturated lactone moiety or an α,β -unsaturated carboxylic acid moiety.

3. A consumer product according to claim 2, which is a fine perfume, a cologne, an after-shave lotion, a liquid or solid detergent, a fabric softener, a fabric refresher, an ironing water, a paper, a bleach, a shampoo, a coloring preparation, a hair spray, a vanishing cream, a deodorant or anti-perspirant, a soap, a shower or bathroom mousse, an oil or gel, a hygiene product, an air freshener, or a wipe.

4. A method of perfuming an article or surface comprising treating the article or surface with a selenide derivative of a fragrance compound comprising an α,β-unsaturated aldehyde moiety, an α,β-unsaturated ketone moiety, an α, -unsaturated ester moiety, an α,β-unsaturated lactone moiety, or an α,β -unsaturated carboxylic acid moiety.

5. A consumer product according to claim 2, wherein the selenide derivative has chemical formula: ##STR00056## wherein X is a group generating the fragrance compound by elimination of an ambient oxidation product of the group Se — R; and wherein R is a C.sub.1-20 linear, cyclic or branched chain alkyl group or a C.sub.6-10 unsubstituted or substituted aryl or heteroaryl group, wherein the substituent is a C.sub.1-12 linear, cyclic or branched chain alkyl group; preferably wherein R is a C.sub.5-16 linear alkyl group, more preferably wherein R is a C.sub.10-14 linear alkyl group, most preferably a C.sub.12 linear alkyl group.

6. A, consumer product according to claim 5, wherein the selenide derivative has chemical formula: ##STR00057## or wherein R.sup.1 is a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl, alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group, optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy group or a C.sub.1-12 alkoxy group; or R.sup.1 is a group — OR.sup.5, wherein R.sup.5 is a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl, alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group, optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy group, or a C.sub.1-12 alkoxy group; and R.sup.2, R.sup.3, R.sup.4 are independently a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy or a C.sub.1-12 alkoxy group; or at least two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are bonded together to form a saturated or unsaturated C.sub.5-20 carbocyclic ring including the carbon atoms to which the at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are attached, the ring being optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear, cyclic or branched chain alkyl or alkene group; or when R.sup.1 is the group —OR.sup.5, R.sup.5 and one of R.sup.2, R.sup.3 and R.sup.4 are bonded together to form a saturated or unsaturated C.sub.4-19 lactone ring including the carbon atoms to which the at least two of R.sup.2, R.sup.3, R.sup.4 and R.sub.5 are attached, the ring being optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear, cyclic or branched chain alkyl or alkene group .sup.4 .

7. A consumer product according to claim 6, wherein R.sup.1 is a hydrogen atom; a C.sub.1-3 linear or branched chain alkyl group; or a C.sub.5-10 cyclic alkene group, optionally substituted with one or more of a substituent comprising a C.sub.1-3 linear or branched chain alkyl or alkene group; and R.sup.2, R.sup.3, R.sup.4 are independently a hydrogen atom; a C.sub.1-5 linear or branched chain alkyl group; or a C.sub.5-10 cyclic alkene group, optionally substituted with one or more of a substituent comprising a C.sub.1-3 linear or branched chain alkyl or alkene group; or at least two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are bonded together to form a saturated C.sub.5-20 carbocyclic ring including the carbon atoms to which the at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are attached, the ring being optionally substituted with one or more of a substituent comprising a C.sub.1-5 linear or branched chain alkyl or alkene group; and the remainder of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are as described above.

8. A consumer product according to claim 6, wherein the selenide derivative has chemical formula: ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## wherein the dotted line indicates the presence of one or two double carbon-carbon bonds between any adjacent pairs of the carbon atoms along which the dotted line extends; R.sup.6 is a hydrogen atom or a methyl group; and R.sup.7 is a hydrogen atom, a hydroxy group, a methoxy group or a linear or branched chain C.sub.1-C.sub.4 alkyl group.

9. A consumer product according to claim 8, wherein the selenide derivative has chemical formula: ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## or ##STR00073## .

10. A compound having the formula: ##STR00074## wherein X is a group generating a fragrance compound comprising an α,β-unsaturated aldehyde, an α,β-unsaturated ketone, an α,β-unsaturated ester, an α,β-unsaturated lactone or an α,β-unsaturated carboxylic acid by elimination of an ambient oxidation product of the group Se — R; and wherein R is a C.sub.5-16 linear, cyclic or branched chain alkyl group, preferably wherein R is a C.sub.10-14 linear alkyl group, more preferably a C.sub.12 linear alkyl group.

11. A compound according to claim 10 of chemical formula: ##STR00075## wherein R.sup.1 is a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl, alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group, optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy group or a C.sub.1-12 alkoxy group; or R.sup.1 is a group — OR.sup.5, wherein R.sup.5 is a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl, alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group, optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy group, or a C.sub.1-12 alkoxy group; and R.sup.2, R.sup.3, R.sup.4 are independently a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy or a C.sub.1-12 alkoxy group; or at least two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are bonded together to form a saturated or unsaturated C.sub.5-20 carbocyclic ring including the carbon atoms to which the at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are attached, the ring being optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear, cyclic or branched chain alkyl or alkene group; or when R.sup.1 is the group —OR.sup.5, R.sup.5 and one of R.sup.2, R.sup.3 and R.sup.4 are bonded together to form a saturated or unsaturated C.sub.4-19 lactone ring including the carbon atoms to which the at least two of R.sup.2, R.sup.3, R.sup.4and R.sup.5 are attached, the ring being optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear, cyclic or branched chain alkyl or alkene group.

12. A compound according to claim 11, wherein R.sup.1 is a hydrogen atom; a C.sub.1-3 linear or branched chain alkyl group; or a C.sub.5-.sub.10 cyclic alkene group, optionally substituted with one or more of a substituent comprising a C.sub.1-3 linear or branched chain alkyl or alkene group; and R.sup.2, R.sup.3, R.sup.4 are independently a hydrogen atom; a C.sub.1-5 linear or branched chain alkyl group; or a C.sub.5-10 cyclic alkene group, optionally substituted with one or more of a substituent comprising a C.sub.1-3 linear or branched chain alkyl or alkene group; or at least two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are bonded together to form a saturated C.sub.5-20 carbocyclic ring including the carbon atoms to which the at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are attached, the ring being optionally substituted with one or more of a substituent comprising a C.sub.1-5linear or branched chain alkyl or alkene group.

13. A compound according to claim 11 , having chemical formula: ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## wherein the dotted line indicates the presence of one or two double carbon-carbon bonds between any adjacent pairs of the carbon atoms along which the dotted line extends; R.sup.6 is a hydrogen atom or a methyl group; and R.sup.7 is a hydrogen atom, a hydroxy group, a methoxy group or a linear or branched chain C.sub.1-C.sub.4 alkyl group.

14. A compound according to claim 13 having chemical formula ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## .

15. A method for the preparation of a selenide derivative of a fragrance compound according to claim 10, comprising an α,β-unsaturated aldehyde moiety, an α,β-unsaturated ketone moiety, an α,β-unsaturated ester moiety, an α,β-unsaturated lactone moiety or an α,β-unsaturated carboxylic acid moiety having the formula ##STR00093## wherein X is a group generating a fragrance compound comprising an α,β-unsaturated aldehyde, an α,β-unsaturated ketone, an α,β-unsaturated ester, an α,β-unsaturated lactone or an α,β-unsaturated carboxylic acid by elimination of an ambient oxidation product of the group Se — R; and wherein R is a C.sub.5-16 linear, cyclic or branched chain alkyl group, preferably wherein R is a C.sub.10-14 linear alkyl group, more preferably a C.sub.12 alkyl group; the method comprising reacting the fragrance compound with an alkyl, aryl or heterocyclic selenide ion formed by treatment of a dialkyl, diaryl or diheterocyclic diselenide with borohydride; wherein the dialkyl, diaryl or diheterocyclic diselenide has chemical formula: ##STR00094## .

16. A method according to claim 15, wherein the α,β-unsaturated aldehyde, ketone, ester, lactone or carboxylic acid moiety has a chemical formula: ##STR00095## wherein R.sub.1 is a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl, alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group, optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy group or a C.sub.1-12 alkoxy group; or R.sup.1 is a group — OR.sup.5, wherein R.sup.5 is a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl, alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group, optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy group, or a C.sub.1-12 alkoxy group; and R.sup.2, R.sup.3, R.sup.4 are independently a hydrogen atom; a C.sub.1-20 linear or branched chain alkyl, alkenyl alkadienyl or alkynyl group; or a C.sub.5-10 cyclic alkyl or cyclic alkene group, each optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl or alkene group; or a C.sub.6-10 aryl group optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear or branched chain alkyl group, a hydroxy or a C.sub.1-12 alkoxy group; or at least two of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are bonded together to form a saturated or unsaturated C.sub.5-20 carbocyclic ring including the carbon atoms to which the at least two of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are attached, the ring being optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear, cyclic or branched chain alkyl or alkene group; or when R.sup.1 is the group —OR.sup.5, R5 and one of R.sup.2, R.sup.3 and R.sup.4 are bonded together to form a saturated or unsaturated C.sub.4-19 lactone ring including the carbon atoms to which the at least two of R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are attached, the ring being optionally substituted with one or more of a substituent comprising a C.sub.1-12 linear, cyclic or branched chain alkyl or alkene group.

Description

[0109] The present disclosure will now be described in more detail by way of Example only with reference to the following Examples and the accompanying drawings in which:

[0110] FIG. 1 is a scheme generally outlining the formation of a β- selenide derivative of an a,β-unsaturated aldehyde, ketone, ester, lactone or carboxylic acid and the regeneration of the a,β-unsaturated aldehyde, ketone, ester, lactone or carboxylic acid in ambient environment;

[0111] FIG. 2 is a scheme outlining the preparation of a β-selenide derivative of a fragrance compound according to one embodiment of the present disclosure; and

[0112] FIG. 3 is a scheme outlining the preparation of an α-selenide derivative of a fragrance compound according to one embodiment of the present disclosure; and

[0113] FIG. 4 is a scheme outlining the regeneration in ambient atmosphere of a fragrance compound according to one embodiment of the present disclosure.

[0114] Referring now to FIG. 1, there is shown a reaction scheme generally illustrating the generation of alkyl selenide ion (RSe.sup.-) from a dialkyl diselenide by treatment with sodium borohydride (NaBH.sub.4) and subsequent reaction (by conjugate addition) of the alkyl selenide ion with an a, β-unsaturated aldehyde, ketone, or ester to form a selenide derivative (at the β position) of the a, β-unsaturated aldehyde, ketone, or ester.

[0115] A suitable method for carrying out the reaction is described by Gelson Perin, Elton L. Borges, Paloma C. Rosa, Patrick N. Carvalho, and Eder João Lenardao in Tetrahedron Letters 54 (2013) 1718-1721.

[0116] Note that 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) may be used in addition to sodium borohydride in order to convert the alkyl selenol (RSeH), a reaction byproduct of sodium borohydride with the dialkyl diselenide, to generate further alkyl selenide ion (RSe.sup.-).

[0117] The reaction scheme also shows the decomposition of the selenide derivative by oxidation and subsequent elimination of the oxidation product to regenerate the a, β-unsaturated aldehyde, ketone, or ester.

[0118] Note that the decomposition may proceed by oxidation to selenoxide or selenone and elimination of either an alkyl seleninic acid or an alkyl selenenic acid.

[0119] The dialkyl diselenide can, for example, be prepared in a one-pot reaction comprising treatment of selenium with sodium borohydride to generate disodium diselenide and subsequent reaction with an alkyl, aryl or heterocyclic bromide.

[0120] One such method for preparing the dialkyl diselenide (as well as diaryl diselenide or diheterocyclic diselenide) is described by Daniel L. Klayman and T. Scott Griffin in J. Am. Chem. Soc. 1973, 95, 1, 197-199.

[0121] Referring now to FIG. 2, there is shown a synthesis of didodecyl diselenide and the preparation of the dodecyl selenide derivative of δ-damascone (δ-(dodecylselenyl)damascone) in accordance with one embodiment of the present disclosure.

[0122] As may be seen, the treatment of didodecyl diselenide with sodium borohydride and DBU in the presence of δ-damascone results in conjugate (Michael) addition at the β-position of the α,β-unsaturated ketone moiety.

[0123] Referring now to FIG. 3, there is shown a reaction scheme generally illustrating the generation of hydrogen atom from tri-n-butyl tin hydride and its subsequent addition to δ-damascone at the β-position of the α,β-unsaturated ketone moiety. The addition leads to a comparatively stable radical at the a-position of the ketone moiety which is quenched by the addition of an alkyl (or other) selenol so that an alkyl (or other) selenide group is formed at the a-position.

[0124] Note that the radical may also be quenched by an alkyl thiol and that the a-sulfide derivative so obtained may be of some value as compared to the β-sulfide derivative for the controlled release of δ-damascone.

[0125] Referring now to FIG. 4, there is shown a reaction scheme generally describing the decomposition of the dodecyl selenide derivative of δ-damascone in ambient environment to regenerate δ-damascone.

[0126] The decomposition of 5-(dodecylselenyl)damascone in ambient is thought to proceed through oxidation by air to selenoxide and thence selenone and elimination of an alkyl seleninic acid.

[0127] However, as mentioned above, the decomposition may also proceed through oxidation to selenoxide and elimination of an alkyl selenenic acid.

[0128] The following examples describe in detail the preparation of δ-(dodecylselenyl)damascone, a fragrance composition comprising δ-(dodecylselenyl)damascone, and a fabric softener comprising the fragrance composition.

Example 1 - Preparation of Dodecyl Selenide Derivative of δ-Damascone Preparation of Didodecyl Diselenide

[0129] Didodecyl selenide was prepared in line with the method described by Daniel L. Klayman and T. Scott Griffin in J. Am. Chem. Soc. 1973, 95, 1, 197-199.

[0130] To a suspension of selenium (2.5 g; 31.6 mmol) in ethanol (30 ml), 2.4 g (63.3 mmol) of NaBH.sub.4 were added and the mixture stirred at room temperature. Considerable foaming (due to H.sub.2) occurred immediately in the vigorous reaction and the selenium was consumed in less than 20 min. Then, others 2.5 g (31.6 mmol) of selenium were added and the mixture was stirred 10 min more. The formation of sodium diselenide was confirmed by TLC. Then, 15.7 g (63.3 mmol) of dodecyl bromide were added and the mixture was stirred at room temperature for 24 hr. The reaction progress was followed by TLC. Once the reaction was completed, the solvent was evaporated and the crude extracted with hexane (20 ml), filtered and dried over Na.sub.2SO.sub.4 and the solvent evaporated under reduced pressure. Yield of crude product: 17.2 g (83%).

Preparation of 3-(Dodecylselenyl)-1-(2,6,6-Trimethyl-3-Cyclohexen-1-yl)-1-Butanone

[0131] The β-dodecyl selenide derivative of δ-damascone was prepared in line with the method described by Gelson Perin, Elton L. Borges, Paloma C. Rosa, Patrick N. Carvalho, and Eder João Lenardao in Tetrahedron Letters 54 (2013) 1718-1721.

[0132] To a mixture of didodecyl diselenide prepared as above (5 g; 10.07 mmol) in THF (30 ml), under nitrogen atmosphere, δ-damascone (5.8 g; 30.21 mmol), NaBH.sub.4 (0.38 g; 10.07 mmol) and DBU (1.53 g; 10.07 mmol) were added and the mixture was stirred at room temperature, following the reaction progress by TLC. After 2 h of reaction, the solution was cooled to room temperature, diluted with ethyl acetate (20 ml) and washed with water (3 x 10 ml). The organic phase was separated, dried over Na.sub.2SO.sub.4 and the solvent evaporated under reduced pressure. Yield of crude product: 10.1 g (93.5 %).

[0133] The β-dodecyl selenide derivative was isolated by column chromatography using hexane or hexane/ethyl acetate as eluent - and characterized as follows: 1H-NMR: 0.80-0.90 (m, 6H); 0.90-1.05 (m, 6 H); 1.25 (m, 18 H); 1.42 (d, 3 H); 1.68 (m, 2 H); 1.89 (m, 1 H); 1.96 (dd, 1 H); 2.22 (dd, 1 H); 2.58-3.07 (m, 4 H); 3.42 (m, 2 H); 5.47 (m, 1 H); 5.56 (m, 1 H). 13C-NMR: 213.6 (Cq); 132.3 (CH); 124.6 (CH); 63.5 (CH); 56.1 (CH.sub.2); 42.6 (CH2); 33.5 (CH); 32.2 (CH.sub.3); 30.8-29.2 (Several CH.sub.2); 27.2 (CH); 24.6 (Cq); 22.6 (CH.sub.3); 20.5 (CH.sub.3); 19.8 (CH.sub.3); 14.8 (CH.sub.3). 77Se—NMR— 286.77 ppm MS-GM Spectrometry:

[00001]$\left[\text{M+1}\right]=442$

Example 2 - Fragrance Compositions

[0134] A fragrance composition (hereinafter designated “Example Composition 1”) was prepared by adding the β-dodecyl selenide derivative of δ-damascone (of Example 1) to a standard fragrance base at a concentration of 5% w/v. The composition of the Example Composition 1 is shown in Table 1 (the β-dodecyl selenide derivative of δ-damascone is labelled “TEST COMPOUND”.

[0135] Additional fragrance compositions were prepared by replacing the β-dodecyl selenide derivative of δ-damascone in the composition of Table 1 of by 5% w/v δ-damascone (hereinafter “δ-damascone (-)”) and 5% w/v of the β-dodecyl sulfide derivative of δ-damascone (prepared as described in WO 03/049666 A2; hereinafter “competitor (S)”).

TABLE-US-00001 Compound % w/v CAS N° GALAXOLIDE IPM MUI 9.00 1222-05-5 CYCLOVERDYL ACETATE MUI 8.00 2500-83-6 LILESTRALIS MUI 8.40 80-54-6 CITRONELLOL MUI 7.80 106-22-9 ROSE CRYSTALS MUI 7.00 90-17-5 TERPINEOL 95 MUI 6.70 98-55-5 ISOBORNYL ACETATE MUI 6.30 125-12-2 DIPROPYLENE GLYCOL MUI 5.70 25265-71-8 ALLYL PHENOXYACETATE 4.60 7493-74-5 DIPHENYL OXIDE MUI 4.45 101-84-8 DIHYDROTERPINYL ACETATE MUI 3.70 58985-18-5 BENZYL ACETATE FG MUI 3.36 140-11-4 TERPINEOL DBCH PERFUMERY MUI 2.80 98-55-5 P-TERBUTYLCYCLOHEXYL ACETATE MUI 2.61 32210-23-4 DIMETHYL OCTANOL / TETRAHYDROGERANIOL MUI 2.50 106-21-8 LINALOOL MUI 2.20 78-70-6 LAVANDIN GROSSO OIL MUI 1.60 8022-15-9 PHENYLETHYL ACETATE K MUI 1.40 103-45-7 ALDEHYDE C14 / GAMMA-UNDECALACTONE FG MUI 1.00 104-67-6 PHENYLPROPYL ALCOHOL MUI 1.00 122-97-4 GERANIOL EXTRA 97% MUI 0.90 106-24-1 NEROL EXTRA FG MUI 0.90 106-25-2 METHYL IONONE MUI 0.60 1335-46-2 CITRONELLYL ACETATE MUI 0.50 150-84-5 LINALYL ACETATE MUI 0.50 115-95-7 PHENETHYL ALCOHOL MUI 0.20 60-12-8 BUTYLATED HYDROXYTOLUENE MUI 0.10 128-37-0 MYRCENATE MUI 0.20 25225-08-5 EUCALYPTOL NATURAL FG K MUI 0.10 470-82-6 DIMETHYL MYRCETONE MUI 0.10 54464-57-2 L-BORNEOL CRYSTALS 64% PURITY MUI 0.10 464-45-9 DIHYDROMYRCENOL K MUI 0.10 18479-58-8 CAMPHOR 96% SYNTH MUI 0.10 76-22-2 GURJUM BALSAM MUI 0.10 8030-55-5 KOAVONE MUI 0.10 81786-73-4 GERANIUM OIL, EGYPT FG MUI 0.10 8000-46-2 COUMARIN MUI 0.10 91-64-5 P-METHYLACETOPHENONE FG MUI 0.02 122-00-9 METHYL HEXYL CETONE FG MUI 0.02 111-13-7 TEST COMPOUND 5.00 n/a CITRONELLAL MUI 0.01 106-23-0 HEXYL ACETATE FG K MUI 0.01 142-92-7 ETHYL AMYL CETONE FG MUI 0.01 106-68-3 CITRONELLYL FORMATE FG MUI 0.01 105-85-1 100.00

Example 3 - Performance of Example Composition 1 in a Fabric Softener

[0136] The performance of Example Composition 1 (of Example 2) in a standard fabric softener base (see Example 4) was evaluated in accordance with an industry standard panel evaluation test. The additional fragrance compositions comprising δ-damascone (δ-damascone (-)) and the β-dodecyl sulfide derivative of δ-damascone (competitor (S)) were also evaluated in the same test.

[0137] The fabric softeners were prepared by mixing the respective fragrance compositions into the standard fabric softener composition. The procedure is illustrated in Example 4 (the standard fabric softener base being everything other than the fragrance composition).

[0138] The panel was made up of seven expert professionals (perfumers and evaluators) and the evaluation performed (in a room substantially free from ambient odors) on the fabric softener and samples of fabrics of similar size washed (and dried) with the fabric softeners at the same time.

[0139] Each of the fabric softeners and samples (not more than five at any one time) was labeled with a random code having a correspondence with a fragrance composition not known to the panel.

[0140] The panellists were asked to rate liking and strength of the fragrance softener and the fabric samples according to the following key:

TABLE-US-00002 Liking: Strength: 1. Disliked 1. Very weak 2. Neither Liked nor disliked 2. Weak 3. Fair 3. Medium Strength 4. Good 4. Strong 5. Very good 5. Very strong

[0141] Three different fabrics types (100% cotton, combination of 60% cotton and 40% polyester, 100% polyester (comprising a mixture of contaminated and uncontaminated fabrics providing half-load ∼ 2 kg) were washed with fabric softener in respective washing machines (all the same brand and model). The fabric softeners and the washed fabrics were presented for evaluation by the panel in accordance with the following procedure:

Phase 1: Wet Fabrics

[0142] The fabric softener was dispensed from a compartment of the washing machine on commencement of a wash cycle at room temperate which lasted 30 minutes. After the completion of the wash cycle the just washed fabric samples were evaluated as described above.

Phase 2: Fabric Softener

[0143] 10 g of each fabric softener was placed in a respective wide mouth glass jar and the neat fabric softener evaluated as described above.

Phase 3: Dry Fabrics

[0144] The washed fabric samples (from phase 1) were hung up on respective clothes lines to dry (at room temperature) and left there during a period of ten days. The dried fabrics were evaluated as described above every two days up to 10 days.

[0145] The averaged results of the evaluation by the panel for the just washed and dried fabric samples are summarized in Table 2.

[0146] As may be seen from Table 2, the performance of Example Composition 1 in the fabric softener is from the outset generally superior to that of Competitor (S) in liking, and is superior in duration to both Competitor (S) and δ-damascone.

[0147] Without wishing to be bound by theory, it is thought that the superiority of the β-selenide is because the oxidation of selenide in ambient environment proceeds to a greater extent of completion as compared to the oxidation of sulphide on account of the accessibility of the significantly larger selenium atom as compared to sulphur atom.

TABLE-US-00003 Period Sample Averaged Liking Averaged Strength 0 Days Competitor (S) 3.31 3.36 Example Composition 1 3.44 3.20 δ-Damascone (-) 3.46 3.11 2 Days Competitor (S) 3.37 3.33 Example Composition 1 3.51 3.31 δ-Damascone (-) 2.50 1.69 3 Days Competitor (S) 3.64 3.00 Example Composition 1 3.62 3.26 δ-Damascone (-) 2.40 1.40 4 Days Competitor (S) 3.21 2.86 Example Composition 1 3.40 2.97 δ-Damascone (-) 1.43 1.07 7 Days Competitor (S) 3.06 2.93 Example Composition 1 3.36 3.18 δ-Damascone (-) 1.20 0.75

Example 4 - Fabric Softener

[0148] A fabric softener (see Table 3) comprising Example Composition 1 of Example 2 was prepared as follows:

[0149] A solution of the dye in deionised water was prepared by addition of the dye with stirring to deionised water heated to 55° C. Pre-heated (to 45° C.) dehydrogenated tallowoylethyl hydroxyethylmonium metho-sulfate was added to this solution slowly with stirring and the stirring continued until the mixture had cooled to room temperature (around 20 mins). Calcium chloride dihydrate salt diluted with a little deionised water was added to the resulting mixture and the stirring continued for further 10 minutes. Isothiazolinone preservative and Example Composition 1 was added and the resulting mixture thoroughly stirred for a further 15 minutes.

TABLE-US-00004 Ingredient (INCI Name) % W/W Dihydrogenated tallowoylethyl hydroxyethylmonium methosulfate 16.4 Methyl-4-isothiazolin 2.5% and 1,2-Benzisothiazolin-3-one 2.5% 0.1 CaCl.sub.2.2H.sub.20 (15% in water) q.s. Dye (10% in water) q.s. Example Composition 1 1.0 Deionised water to 100

Example 5 - Preparation of 3-(Dodecylselenyl)-1-(2,6,6-Trimethyl-2-Cyclohexen-1-yl)-1-Butanone

[0150] The β-dodecyl selenide derivative of a-damascone was synthesized from α-damascone and didodecyl diselenide following the procedure of Example 1.

[0151] The β-dodecyl selenide derivative was isolated by column chromatography using hexane or hexane/ethyl acetate as eluent and characterized as follows:

[0152] 1H-NMR: 0.84-0.95 (m, 12 H); 1.25 (br, 18 H); 1.45 (dd, 3H); 1.55-2.25 (m, 6 H); 2.35-2.80 (m, 3 H); 2.83 (d, 1 H); 3.45 (m, 2 H); 5.59 (br, 1 H). 13C-NMR: 212.2 (Cq); 130.2 (Cq); 123.7 (CH); 64.1 (CH); 54.5 (CH2); 47.5 (CH2); 33.0-27.5 (many, Cq, CH2); 28.2 (CH3); 24.0 (CH3); 23.6 (CH2); 23.5 (CH3); 14.1 (CH3).

##STR00045##

[0153] MS-GM Spectrometry:

##STR00046##

[0154] The derivative has the same fragrance profile as the original alpha-damascene with a distinctive floral fruity note with a touch of apple and blackcurrant.

Example 6 - Preparation of 3-(Dodecylselenyl)-1-(2,6,6-Trimethyl-1,3-Cyclohexadien-1-yl)-1-Butanone

[0155] The β-dodecyl selenide derivative of β-damascenone was synthesized from β-damascenone and didodecyl diselenide following the procedure of Example 1.

[0156] The β-dodecyl selenide derivative was isolated by column chromatography using hexane or hexane/ethyl acetate as eluent and characterized as follows:

[0157] 1H-NMR: 0.89 (t, 3 H); 0.97 (t, 3 H); 1.15 (t, 3 H); 1.27 (br, 18 H); 1.50 (d, 3H); 1.65 (m, 2 H); 1.72 (d, 3 H); 2.50-2.65 (dt, 2 H); 2.80-3.00 (m, 3 H); 3.52 (m, 2 H); 5.56 (d, 1 H); 5.62 (m, 1 H).

[0158] 13C-NMR: 208.0 (Cq); 142.4 (Cq); 141.7 (Cq); 128.2 (CH); 127.5 (CH); 54.0 (CH2); 47.5 (CH2); 39.8 (CH2); 34.0-29.3 (many, Cq, CH2); 27.6 (CH); 26.3 (CH3); 27.0 (CH2); 22.9 (CH3); 22.8 (CH2); 19.2 (CH3); 14.3 (CH3).

##STR00047##

[0159] MS-GM Spectrometry:

##STR00048##

[0160] The derivative is very powerful and similar to the β-damascenone typical scent of plum, rose and tobacco.

Example 7 - Preparation of 4-(Dodecylselenyl)-4-(2,6,6-Trimethyl-2-Cyclohexadien-1-yl)-2-Butanone

[0161] The β-dodecyl selenide derivative of a-ionone was synthesized from a-ionone and didodecyl diselenide following the procedure of Example 1.

[0162] The β-dodecyl selenide derivative was detected by Gas Cromatography and confirmed by Mass Spectroscopy.

[0163] MS-GM Spectrometry:

##STR00049##

[0164] The derivative has a very similar fragrance profile to a-ionone, with a warm and woody character with a touch of violet flowers.

Example 8 - Preparation of 3-(Dodecylselenyl)-Hexanal

[0165] The β-dodecyl selenide derivative of trans-2-hexenal was synthesized from trans-2-hexenal and didodecyl diselenide following the procedure of Example 1. The β-dodecyl selenide derivative was detected by Gas Chromatography and confirmed by Mass Spectroscopy.

[0166] MS-GM Spectrometry:

##STR00050##

[0167] The derivative maintains the same profile, fruity green, as the trans-2-hexenal during the first 48 hours, and after that the smell changes to a pleasant grapefruit with lemon notes.

Example 9 - Preparation of 8a-(Dodecylselenyl)-4,4a-Dimethyl-6-(Prop-1-en-2-yl)-4,4a,5,6,7,8-Hexahydro-Naphthalen-2-One

[0168] The β-dodecyl selenide derivative of nootkatone was synthesized from nootkatone and didodecyl diselenide following the procedure of Example 1. The β-dodecyl selenide derivative was detected by Gas Chromatography and confirmed by Mass Spectroscopy.

[0169] MS-GM Spectrometry:

##STR00051##

[0170] The derivative has the same fragrance profile as the original Nootkatone, with an intensive grapefruit, citrus and lightly woody fragrance.

Example 10 - Preparation of 3-(Dodecylselenyl)-5-Isopropenyl-2-Methylcyclohexanone

[0171] The β-dodecyl selenide derivative of carvone was synthesized from carvone and didodecyl diselenide following the procedure of Example 1. The β-dodecyl selenide derivative was detected by Gas Chromatography and confirmed by Mass Spectroscopy.

[0172] MS-GM Spectrometry:

##STR00052##

[0173] The derivative has a similar fragrance profile as the original Carvone, suit mint and spearmint leaves.

Example 11

Preparation of Dipentyl Diselenide

[0174] Dipentyl selenide compound was synthesized from n-pentyl bromide and selenium following the procedure of Example 1. The product was detected by Gas Chromatography and confirmed by Mass Spectroscopy.

[0175] MS-GM Spectrometry:

##STR00053##

Preparation of 3-(Pentylselenyl)-1-(2,6,6-Trimethyl-3-Cyclohexen-1-yl)-1-Butanone

[0176] The synthesis of the β-pentyl selenide derivative of δ-damascone was performed from δ-damascone and dipentyl diselenide following the procedure of Example 1. The β-pentyl selenide derivative was detected by Gas Chromatography and confirmed by Mass Spectroscopy.

[0177] 1H-NMR: 0.86 (d, 3H); 0.90-1.10 (m, 9H); 1.30-1.50 (m, 4 H); 1.60-1.80 (m, 2H); 1.91 (d, 3H); 1.98 (m, 1H); 2.22 (dd, 2H); 2.48 (d, 1H); 2.55-2.72 (m, 2H); 2.80-3.05 (m, 3H); 5.40-5.60 (m, 1H); 6.23 (dd, 1H).

[0178] 13C-NMR: 203.9 (Cq); 132.3 (CH); 124.2 (CH); 60.3 (CH); 55.5 (CH.sub.2); 42.1 (CH.sub.2); 31.5 (CH); 30.1 (CH.sub.2); 29.9 (CH.sub.3); 23.2 (CH.sub.2); 22.6 (Cq); 21.1 (CH.sub.3); 20.7 (CH.sub.3); 18.4 (CH.sub.3); 14.1 (CH.sub.3).

##STR00054##

[0179] MS-GM Spectrometry:

##STR00055##

[0180] The derivative has the same fragrance profile as the original Delta Damascone with an intense Rose, floral woody and slightly citrus and herbal notes.

Example 12 - Preparation of Example Compositions 5, 6 and 8

[0181] The α-damascone derivative of Example 5, β-damascenone derivative of Example 6 and the trans-2-hexenal derivative of Example 8 were each used to prepare fragrance compositions (hereinafter designated “Example Composition 5”, “Example Composition 6” and “Example Composition 8” respectively). The fragrance compositions were prepared by adding 5% w/v of the respective derivative to the reference fragrance composition used in Example 2, but using 5% w/v of the derivative as the “TEST COMPOUND” to replace the β-dodecyl selenide derivative of δ-damascone.

Example 13 - Performance of Example Compositions 5, 6 and 8 in a Fabric Softener

[0182] The performances of Example Compositions 5, 6 and 8 were compared in the standard fabric softener base of Example 4. In each case, 1%w/w of the respective Example Composition was used instead of Example Composition 1.

[0183] The fabric softeners were evaluated using the procedure set out in Example 3, although the evaluation panel was made up of 9 expert professionals (perfumers and evaluators) rather than 7.

[0184] The fabric softeners were each used to wash three different fabric types, as set out in example 3, and the panellists were asked to rate liking and strength of the fabric softeners and washed fabrics using the according to the key set out in Example 3.

[0185] The average results for the evaluation by the panel of the fabric softeners comprising each Example Composition are set out in Table 4.

TABLE-US-00005 Sample Averaged Liking Averaged Strength Example Composition 5 3.44 3.57 Example Composition 6 3.63 3.87 Example Composition 8 3.49 3.78

[0186] The average results for the evaluation by the panel of the just washed (wet) fabric samples and the dried fabric samples are set out in Table 5.

TABLE-US-00006 Period Sample Averaged Liking Averaged Strength 0 Days (wet) Example Composition 5 3.44 3.34 Example Composition 6 3.66 3.67 Example Composition 8 3.37 3.63 1 Day Example Composition 5 3.52 3.52 Example Composition 6 3.6 3.51 Example Composition 8 3.66 3.58 Example Composition 5 3.61 3.32 Example Composition 6 3.65 3.40 Example Composition 8 3.70 3.44 Example Composition 5 3.40 3.42 Example Composition 6 3.56 3.58 Example Composition 8 3.68 3.52

[0187] The Examples demonstrate the suitability of the selenide derivatives of fragrance compounds to provide for long lasting controlled release of the fragrance compound.

[0188] They also show that the selenide derivatives provide that the fragrance composition has a note which is cleaner (or clearer) than that of the corresponding sulfide derivative and also that the release of the fragrance may be longer lasting than for the corresponding sulfide derivative.

[0189] The fragrance on a fabric article treated with a fabric softener containing the selenide derivative can persist for a period of at least three days, for example at least 5 days, at least 10 days, at least 21 days, at least 35 days or even longer.