Fragrance compounds

Abstract

A method of providing a fragrant odour to an application, comprising the addition thereto of at least one compound of the formula I ##STR00001##
wherein X and Y are independently selected from the group consisting of CR.sup.1R.sup.2R.sup.3, NR.sup.4R.sup.5 and OR.sup.6, wherein R.sup.1 to R.sup.5 are selected from H and essentially hydrocarbon moieties that optionally comprise at least one oxygen, nitrogen or silicon atom, and R.sup.6 is selected from essentially hydrocarbon moieties that optionally comprise at least one oxygen, nitrogen or silicon atom; and, A is an essentially hydrocarbon moiety that optionally comprises at least one oxygen, sulphur, nitrogen or silicon atom, with the proviso that the compound A-CHO is a fragrant aldehyde. The use of these compounds in laundry, household and personal care products confers a long-lasting freshness.

Claims

1. A composition comprising animal litter material and at least one compound of Formula I: ##STR00023## wherein X is methyl, Y is oxyethyl, and A is selected from ##STR00024## wherein the at least one compound of Formula I is present at a level effective to provide a reduced urine malodour effect.

2. The composition according to claim 1, wherein the compound of Formula I is ethyl 2-acetyl-5-(-4-(tert-butyl)phenyl)-4-methylpent-2-enoate.

3. The composition according to claim 1, wherein the compound of Formula I is ethyl 2-acetyl-5-(3 -isopropylphenyl)hex-2-enoate.

4. The composition according to claim 1, wherein the compound of Formula I is ethyl 2-acetyl-4-methyltridec-2-enoate.

5. The composition according to claim 1, wherein the compound of Formula I is present at a level from about 0.05% to about 5% by weight of the litter material.

6. The composition according to claim 1, wherein the compound of Formula I is present at a level from about 0.1% to about 0.5% by weight of the litter material.

7. A method for reducing malodour impression on animal litter material comprising applying to the litter material from about 0.05% to about 5% by weight of the litter material, at least one compound of Formula I: ##STR00025## wherein X is methyl, Y is oxyethyl, and A is selected from ##STR00026##

8. The method according to claim 7, wherein the compound of Formula I is ethyl 2-acetyl-5-(-4-(tert-butyl)phenyl)-4-methylpent-2-enoate.

9. The method according to claim 7, wherein the compound of Formula I is ethyl 2-acetyl-5-(3-isopropylphenyl)hex-2-enoate.

10. The method according to claim 7, wherein the compound of Formula I is ethyl 2-acetyl-4-methyltridec-2-enoate.

11. The method according to claim 7, comprising applying to the litter material from about 0.1% to about 0.5% by weight of the litter material, to the at least one compound of Formula I.

Description

EXAMPLE 1

Preparation of 2-benzoyl-dec-2-enoic acid ethyl ester, a compound according to the formula

(1) ##STR00011##

(2) Piperidine (0.10 ml, 0.5 mol %) is added to a mixture of octanal (25.6 g, 0.20 mol) and ethyl benzoylacetate (38.4 g, 0.20 mol) at 5 C. The resulting solution is warmed to room temperature and stirred for 24 h, during which a fine emulsion is formed. The mixture is diluted with methyl t-butyl ether and the organic layer washed with 2 N aq. HCl-solution, water and brine, then dried over MgSO.sub.4.

(3) The solvent is removed in vacuo and the residue distilled to yield 18.0 g (38%) of product as an E/Z-mixture, boiling at 129-135 C./0.1 mbar.

(4) .sup.13C-NMR (CHCl.sub.3, 100 MHz; main isomer): 194.5 (s), 164.6 (s), 148.6 (d), 137.2 (s), 133.7 (d), 133.6 (s), 129.0 (d), 128.8 (d), 61.0 (t), 31.6 (t), 29.5 (t), 29.1 (t), 28.8 (t), 28.3 (t), 22.5 (t), 14. (q), 13.9 (q).

(5) MS (EI, 70 eV): 302 (<1, M.sup.+), 257 (2), 217 (10), 199 (15), 186 (15), 171 (4), 157 (13), 105 (100).

EXAMPLES 2-12

(6) The following compounds are made by a method according to claim 1, using the appropriate fragrant aldehyde and 1,3-dicarbonyl compound:

(7) TABLE-US-00002 b.p. (if distilled) .sup.13C-NMR [ C./ CDCl.sub.3, 100 MHz MS N Structure mbar] (only main isomer) EI, 70 eV 2 127/0.07 194.9 (s), 166.5 (s), 147.5 (d), 139.8 (s), 131.6 (s), 124.2 (d), 59.4 (t), 39.5 (t), 35.3 (t), 32.3 (d), 27.4 (t), 25.7 (q), 22.4 (q), 19.6 266 (29, M.sup.+), 221 (27), 205 (26), 177 (29), 149 (20), 43 3 168- 171 C./ 0.08 195.0 (s), 168.8 (s), 149.3 (d), 136.6 (s), 71.8 (t), 70.4 (t), 68.9 (t), 63.5 (t), 58.9 (q), 32.5 (t), 30.0 (t), 29.2 (t), 29.0 (t), 27.0 (t), 22.5 (t), 27.0 (q), 14.0 272 (<1), 239 (7), 195 (17), 137 (45), 124 (27), 59 (94), 45 (100). (q). 4 (purified by chromato- graphy) 194.1 (s), 192.8 (s), 163.9 (s), 156.2 (s), 147.9 (d), 141.9 (s), 133.3(s), 131.7 (d), 130.3 (s), 129.5 (d), 125.4 (d), 13.7 (d), 55.5 (q), 35.1 (s), 31.6 (t), 31.1 (q), 31.0 (t), 31.0 (t), 29.2 (t), 28.9 (t), 22.5 (t), 14.0 (q). 420 (24, M.sup.+), 363 (95), 335 (39), 279 (36), 255 (35), 161 (91), 150 (97), 135 (100). 5 (purified by chromato- graphy) 165.3 (s), 163.8 (s), 151.1 (d), 135.6 (s), 135.4 (s), 128.5 (d), 128.4 (d), 128.3 (d), 128.2 (d), 128.0 (d), 128.0 (d), 67.0 (t), 66.9 (t), 31.7 (t), 29.9 (t), 29.2 (t), 28.9 (t), 28.3 (t), 22.6 (t), 14.1 (q). 394 (5, M.sup.+), 200 (16), 197 (20), 179 (77), 123 (15), 109 (12), 91 (100). 6 (purified by chromato- graphy) 166.8 (s), 166.2 (s), 155.3 (d), 127.3 (s), 52.3 (q), 31.6 (t), 30.4 (t), 30.0 (t), 29.2 (t), 28.9 (t), 22.6 (t), 14.0 (q). 227 (3, M.sup.+), 210 (19), 178 (39), 168 (37), 153 (62), 139 (65), 113 (92), 81 (93), 41 (100). 7 (purified by chromato- graphy) m.p. 126- 128 C. 206.4 (s), 196.4 (s), 148.4 (s), 146.0 (s), 140.6 (s), 140.1 (d), 125.0 (s), 125.0 (d), 114.9 (d), 112.2 (d), 64.6 (t), 31.7 (q), 26.3 (q), 14.7 (q). 248 (30, M.sup.+), 233 (8), 219 (4), 205 (11), 191 (11), 177 (11), 163 (25), 145 (11), 43 (100). 8 (purified by chromato- graphy, only Z- isomer described) 201.2 (s), 164.4 (s), 152.3(d), 149.2 (s), 136.3 (s), 134.9 (s), 128.9 (d), 125.2 (d), 61.1 (t), 42.4 (t), 36.5 (d), 34.4 (s), 31.3 (q), 30.5 (q), 19.9 (q), 14.1 (q). 316 (<1, M.sup.+), 298 (3), 270 (8), 147 (100). 9 (purified by chromato- graphy) 165.4 (s), 164.1 (s), 152.9 (d), 152.6 (d), 148.9 (s), 135.8 (s), 135.6 (s), 129.0 (d), 128.8 (d), 128.7 (d), 128.6 (d), 128.2 (d), 127.8 (d), 127.7 (d), 125.2 (d), 76.2 (d), 61.1 (t), 41.6 (t), 41.6 (t), 41.2 (s, 1 C), 41.1 (t), 39.1 (t), 39.0 (t), 38.3 (d), 38.2 (d), 38.2 456 (2, M.sup.+), 318 (7), 300 (11), 147 (100). (d), 36.1 (d), 35.8 (d), 34.3 (s), 33.5 (q), 33.4 (q), 31.3 (q), 30.5 (s), 30.5 (s), 30.4 (s), 28.3 (t), 28.3 (t), 24.5 (q), 21.9 (t), 21.9 (t), 19.1 (q), 18.9 (q), 17.1 (q), 17.0 (q), 14.1 (q) 10 0 (purified by chromato- graphy) (only E-isomer described) 195.0 (s), 166.3 (s), 149.1 (s), 146.8 (d), 145.3 (s), 137.6 (s), 128.5 (d), 125.1 (d), 124.5 (d), 123.9 (d), 61.1 (t), 39.5 (d), 38.3 (t), 34.1 (d), 26.8 (q), 24.0 (q), 21.6 (q), 14.1 (q). 302 (<1, M.sup.+), 256 (9), 228 (5), 213 (5), 172 (9), 147 (100), 105 (20), 91 (14). 11 (purified by chromato- graphy) (mixture of E and Z- isomers) 201.2 (s), 195.1 (s), 166.6 (s), 164.5 (s), 153.6 (d), 153.4 (d), 135.8 (s), 134.4 (s), 61.1 (t), 61.1 (s), 36.5 (t), 36.5 (t), 34.9 (d), 34.0 (d), 31.8 (t), 31.3 (t), 29.6 (t), 29.5 (t), 29.4 (t), 29.2 296 (<1, M.sup.+), 281 (2), 250 (71), 151 (42), 143 (26), 137 (50), 124 (18), 43 (100). (t), 27.4 (t), 27.3 (t), 26.8 (q), 22.6 (t), 20.1 (q), 19.8 (q), 14.1 (q), 14.1 (q), 14.0 (q). 12 (purified by chromato- graphy) 165.7 (s), 164.0 (s), 154.2 (d), 127.3 (s), 61.1 (t), 61.1 (t), 36.4 (t), 34.7 (d), 31.8 (t), 29.5 (t), 29.5 (t), 29.2 (t), 27.3 (t), 22.6 (t), 19.8 (q), 14.1 (q), 14.0 (q). 326 (<1, M.sup.+), 311 (<1), 297 (<1), 281 (23), 253 (4), 234 (100), 199 (9), 173 (59), 160 (62), 141 (41), 122 (85), 108 (86). (*) The product contains ca. 15% of 2-(1-hydroxy-ethylidene)-dec-3-enoic acid 2-(2-methoxy-ethoxy)-ethyl ester. The starting material, 3-oxo-butyric acid 2-(2-methoxy-ethoxy)-ethyl ester, is prepared as follows:

(8) Ethyl acetoacetate (39.0 g, 0.30 mol) and diethyleneglycol monomethyl ether (36.0 g, 0.30 mol) are heated to 110 C. (oil bath temperature) and tetraisopropyl orthotitanate (0.60 ml, 2.0 mmol, 0.7 mol %) is added. The temperature is further increased to 150 C. After 30 min methanol (5 g) is distilling off and collected. The temperature is maintained for further 8 h while lowering the pressure in the apparatus to 800 mbar. After cooling to room temperature, the residue is distilled at 65-120 C./0.06 mbar to isolate 30.5 g of product containing ca. 10% of diethyleneglycol monomethyl ether (yield 44%).

(9) .sup.13C-NMR (CHCl.sub.13, 100 MHz): 200.4 (s), 167.0 (s), 89.9 (d), 71.8 (t), 70.4 (t), 68.8 (t), 64.2 (t), 59.0 (q), 50.0 (t), 30.0 (q).

(10) MS (EI, 70 eV): 302 (<1, M.sup.+), 257 (2), 217 (10), 199 (15), 186 (15), 171 (4), 157 (13), 105 (100).

EXAMPLE 13

Application in Fabric Softener

(11) To each of two samples of a standard unperfumed fabric softener base of the ester quat type is added one of the following: 1) 0.20% wt/wt of 2-methylundecenal 2) 0.32% wt/wt of ethyl 2-acetyl-4-methyltridec-2-enoate (Example 11), equivalent to 0.20% wt/wt of 2-methylundecanal.

(12) These bases are then added to the rinse cycle of a washing machine loaded with cotton terry towels. After centrifugation, the towels are evaluated olfactorily by a panel of trained evaluators. Odour scores are attributed to each towel at the given time, which are as follows: 0 (odourless), 1 (very weak), 2 (weak), 3 (medium), 4 (strong) and 5 (very strong). The arithmetic means of the scores from all evaluators are reported in the following table.

(13) TABLE-US-00003 ethyl 2-acetyl-4- 2-methylundecanal methyltridec-2-enoate wet 5 2.1 1 d 0.3 3.6 2 d 0.9 4 6 d 0.3 3.8

(14) From day 1 to day 6, the towel washed with the fabric softener base containing a compound according to the invention exhibits a strong 2-methylundecanal note, whereas the towels washed with base containing the free aldehyde are almost odourless.

EXAMPLE 14

Application in Liquid Detergent

(15) To each of four samples of a standard unperfumed heavy duty liquid detergent base samples is added one of the following: 1) 0.20% wt/wt of 2-methylundecenal 2) 0.32% wt/wt of ethyl 2-acetyl-4-methyltridec-2-enoate (Example 11), equivalent to 0.20% wt/wt of 2-methylundecanal. 3) 0.20% wt/wt of 3-(3-isopropylphenyl)butanal 4) 0.32% wt/wt of ethyl 2-acetyl-5-(3-isopropylphenyl)hex-2-enoate (Example 10), equivalent to 0.20% wt/wt of 3-(3-isopropylphenyl)butanal)

(16) Four individual 40 C. wash cycles are performed with the above samples, each with a load of cotton terry towels. Odour scores are attributed to the individual towels after time intervals by a panel of trained evaluators as described in example 3. The results are shown in the following table:

(17) TABLE-US-00004 2-methylundecanal ethyl 2-acetyl-4- 3-(3-isopropylphenyl)- 2-acetyl-5-(3- (Aldehyde methyltridec-2- butanal isopropylphenyl)- C12MNA) enoate (Florhydral) hex-2-enoate wet 3.6 1.5 2.3 3.5 1 d 0 2.3 1.0 2.8 2 d 0 2.3 n.d. n.d. 3 d 0 2.4 n.d. n.d.

(18) From wet to day 3, the towels washed with the liquid detergent base comprising a compound according to the invention exhibit a strong 2-methylundecanal note, whereas the towels washed with base containing the free aldehyde are almost weak to odourless. Likewise, the towels washed with 2-acetyl-5-(3-isopropylphenyl)hex-2-enoate exhibit a strong Florhydral note after 1 day on the dry towel, whereas the towel washed with free Florhydral has only a very weak smell.

EXAMPLE 15

Determination of Urine Malodour Reduction in Presence of Precursor

(19) Preparation of Samples: 30g of sand was dosed with 0.25% of one of the following (0.004 g of 2-methylundecanal Aldehyde C12 MNA for Sample 2 and 0.075g of ethyl 2-acetyl-4-methyltridec-2-enoate for Sample 3). Next 5 g of inoculated cat urine was added to the sand and left at room temperature. The urine malodour and fragrance intensity were assessed daily for 6 days.

(20) Testing procedure: The samples were contained in 120 g powder clear glass jars with lids. The test samples were assessed by a group of trained panellists (consisting of 5 individuals). The malodour intensity and fragrance intensity were rated using the Labeled Magnitude Scale (LMS). Mean (Malodour Intensity and Fragrance Intensity) and standard error of the mean (SE) were obtained, where 0 represents No Sensation and 100 represents The Strongest Imaginable Sensation.

(21) TABLE-US-00005 Malodour Fragrance No. Group Time Intensity SE Intensity SE 1 Sand + 3 hrs 83 3.391 0 0.000 Inoculated 24 hrs 68.2 3.353 0 0.000 Cat Urine 48 hrs 86 2.915 0 0.000 (Control) 72 hrs 88.75 6.575 0 0.000 144 hrs 90 4.564 0 0.000 2 Sand + 3 hrs 82 2.708 0 0.000 Inoculated 24 hrs 67 5.831 20 12.247 Cat Urine + 48 hrs 71 5.788 12 12.000 Aldehyde C12 72 hrs 66.25 8.985 0 0.000 MNA 144 hrs 71.25 7.739 0 0.000 3 Sand + 3 hrs 42.5 4.787 43.75 15.326 Inoculated 24 hrs 54 10.654 25.6 15.728 Cat Urine + 48 hrs 43 9.950 34.6 14.288 Precursor 72 hrs 51.25 10.873 40 13.540 144 hrs 58.75 6.575 25 8.660

(22) The above table demonstrates that the precursor according to the present disclosure is effective in reducing the urine malodour while at the same time maintaining a long-lasting fragrance intensity from day 0 to day 6.