1-(bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one o-methyloxime as a fragrance additive

Abstract

The disclosure relates to an oximether possessing powerful green fruity anisic banana olfactory properties. The invention furthermore refers to a method of its production, and to fragrance compositions comprising it.

Claims

1. A perfumed product comprising: a) 1-(bicyclo[2.2.1]hept-5-en-2-yl) ethan-1-one O-methyl oxime; and b) a consumer product base selected from the group consisting of household products, laundry products, body care products, cosmetic products and air care products.

2. The perfumed product of claim 1, wherein the 1-(bicyclo[2.2.1]hept-5-en-2-yl) ethan-1-one O-methyl oxime exhibits green fruity anisic banana olfactory properties.

3. A method of improving, enhancing, or modifying the consumer product base of claim 1, said method comprising the step of: incorporating 1-(bicyclo[2.2.1]hept-5-en-2-yl) ethan-1-one O-methyl oxime into said consumer product base.

4. A fragrance composition comprising: a) 1-(bicyclo[2.2.1]hept-5-en-2-yl) ethan-1-one O-methyl oxime; and b) at least one other known fragrance ingredient selected from the group consisting of essential oils and extracts, alcohols, aldehydes, ketones, ethers, acetals, esters, lactones, macrocycles, and heterocycles.

5. The perfumed product of claim 1, which is a fabric softener.

6. The perfumed product of claim 1, which is a detergent product.

7. The perfumed product of claim 6, which is a powdered detergent product.

8. The perfumed product of claim 1, which is a personal care product.

9. An entrapped perfume comprising: a) 1-(bicyclo[2.2.1]hept-5-en-2-yl) ethan-1-one O-methyl oxime; and b) an entrapment material selected from the group consisting of polymers, capsules, microcapsules and nanocapsules, liposomes, film formers, absorbents, cyclic oligosaccharides and mixtures thereof.

10. The method of claim 3, wherein the enhancement is the provision of an olfactory bloom emanating from the consumer base having comprised within the 1-(bicyclo[2.2.1]hept-5-en-2-yl) ethan-1-one O-methyl oxime.

11. A fragrance composition comprising: a) 1-(bicyclo[2.2.1]hept-5-en-2-yl) ethan-1-one O-methyl oxime; and b) a base material.

12. A fine perfumery product comprising: a) between 0.1 and 30 weight percent of 1-(bicyclo[2.2.1]hept-5-en-2-yl) ethan-1-one O-methyl oxime; and b) the consumer product base of claim 1.

Description

EXAMPLE 1: 1-(BICYCLO[2.2.1]HEPT-5-EN-2-YL)ETHAN-1-ONE O-METHYL OXIME

(1) To a solution of O-methylhydroxylamine hydrochloride (19.3 g, 231 mmol, 1.5 equiv), sodium acetate (17.7 g, 216 mmol, 1.4 equiv) in water (54 mL) was added at room temperature a solution of 1-(bicyclo[2.2.1]hept-5-en-2-yl)ethanone (21.0 g, 154 mmol, 1.0 equiv) in MeOH (54 mL) within 2 minutes. The turbid reaction mixture was heated to 65 C. for 6 hours. Since the starting material was fully consumed according to GC analysis, the reaction mixture was diluted with water (250 mL) and MTBE (300 mL). The organic layer was washed with water (1), sat. NaHCO.sub.3 (1) and brine (2). The combined aqueous layers were washed once with MTBE. The combined organic extracts were dried over M.sub.gSO4, filtered and concentrated under reduced pressure. The crude (26.4 g) was distilled over a 5 cm Vigreux column under reduced pressure (0.07 mbar) to give 1-(bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime (23.0 g, 90% chemical yield) as a colorless oil. This quality was distilled again over a 10 cm Vigreux column at 0.07 mbar to afford 1-(bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime (19.2 g, 75% olfactive yield, mixture of isomers 83:13:4) as a colorless oil (bp 45 C. (0.07 mbar)).

(2) Odor description: green, fruity, anisic banana character. When used at higher concentration the green note becomes more green, fatty violet/watery curcumber.

(3) .sup.1H NMR (400 MHz, CDCl.sub.3, major isomer 90%): 6.13 (dd, J=5.7, 3.1 Hz, 1H), 5.85 (dd, J=5.6, 2.9 Hz, 1H), 3.77 (s, 3H), 3.09-3.04 (m, 1H), 2.88-2.77 (m, 2H), 1.82-1.73 (m, 1H), 1.74 (d, J=0.5 Hz, 3H), 1.45-1.36 (m, 2H), 1.31-1.26 (m, 1H) ppm. .sup.13C NMR (101 MHz, CDCl.sub.3, major isomer): 158.8, 136.9, 132.0, 61.0, 49.4, 46.0, 44.3, 42.4, 27.7, 14.0 ppm. Characteristic signals for second isomer (7%): .sup.1H NMR (400 MHz, CDCl.sub.3): 6.17 (dd, J=5.7, 3.1 Hz, 1H), 5.93 (dd, J=5.7, 2.9 Hz, 1H), 3.820 (s, 3H), 3.49-3.41 (m, 1H), 3.24-3.19 (m, 1H) ppm. Characteristic signals for third isomer (3%): .sup.1H NMR (400 MHz, CDCl.sub.3): 6.15-6.08 (m, 2H), 3.815 (s, 3H) ppm. GC-MS (EI) m/z (%, major isomer: t.sub.R=5.30 min, 90%): 165 (14, [M].sup.+), 134 (21), 100 (47), 91 (30), 77 (20), 68 (21), 66 (100), 65 (22), 58 (33), 42 (37), 39 (29); GC-MS (EI) m/z (%, second isomer: t.sub.R=5.42 min, 7%): 165 (4, [M].sup.+), 100 (78), 99 (12), 91 (16), 68 (23), 66 (100), 65 (15), 58 (28), 42 (23), 39 (22), 27 (11); GC-MS (EI) m/z (%, third isomer: t.sub.R=5.21 min, 3%): 165 (4, [M].sup.+), 134 (49), 100 (94), 99 (17), 91 (23), 68 (22), 66 (100), 65 (22), 58 (34), 42 (39), 39 (29). IR (neat, v/cm.sup.1): 2968m, 2939m, 2897w, 2870w, 1464w, 1439w, 1366m, 1337m, 1275w, 1239w, 1180w, 1134w, 1049s, 906m, 866s, 833m, 818m, 7563, 722s, 639m.

EXAMPLE 2: 1-(BICYCLO[2.2.1]HEPT-5-EN-2-YL)ETHAN-1-ONE O-METHYL OXIME-ENANTIOENRICHED

(4) An enantioenriched quality of 1-(bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime can be made from enantioenriched 1-(bicyclo[2.2.1]hept-5-en-2-yl)ethanone (known in the literature, e.g. Shanker, R. et al., J. Org. Chem. 2008, 73, 212) using the same procedure as reported in Example 1. Such a quality would consist of a blend out of 8 theroretical stereoisomers (endo/exo, E/Z and enantiomers). Those include: (E)-1-((1R,2S,4R)-bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime, (E)-1-((1S,2R,4S)-bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime, (E)-1-((1R,2R,4R)-bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime, (E)-1-((1S,2S,4S)-bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime, (Z)-1-((1R,2S,4R)-bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime, (Z)-1-((1S,2R,4S)-bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime, (Z)-1-((1R,2R,4R)-bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime, (Z)-1-((1S,2S,4S)-bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime.

EXAMPLE 3: FRAGRANCE ACCORD

(5) TABLE-US-00001 parts by weight Compound/Ingredient 1/1000 BENZALDEHYDE 1 BENZYL SALICYLATE 200 CASSYRANE (2-TERT-BUTYL-5-METHYL- 1 2-PROPYL-2,5-DIHYDROFURAN) - DAMASCONE 10 -DECALACTONE 200 GALAXOLIDE 100 (1,3,4,6,7,8-HEXAHYDRO-4,6,6,7,8,8- HEXAMETHYLINDENO(5,6-C)PYRAN) HEXENOL-3-CIS 20 LINALOOL 200 MANZANATE (ETHYL 2-METHYLPENTANOATE) 10 DIPROPYLENE GLYCOL (DPG) 258 Total: 1000

(6) The figurative peach, green, juicy and natural fragrance accord above is intended for application in shower gel, e.g. @ 1 wt %.

(7) By replacing 1 part of DPG with 1-(Bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime of Example 1, the performance of the accord is significantly increased.

(8) The fragrance accord above comprising 1 part of 1-(Bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime when used @ 1 wt % in a shower gel, the performance and the diffusion is significantly increased compared to the fragrance accord without 1-(Bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime.

EXAMPLE 4: BLOOM PERFORMANCE IN SHAMPOO

(9) To a vessel containing 101 warm water (about 30 C. to 32 C.), enclosed in a non-ventilated standard testing booth, 4 ml of a shampoo comprising 0.2% 1-(bicyclo[2.2.1]hept-5-en-2-yl)ethan-1-one O-methyl oxime from Example 1 was added without mixing. The vessel was located 1.3 meter apart from the door of the booth. After 20 minutes a small window, which is located in the door of the testing booth was opened and the bloom performance was assessed by a panel of trained perfumers. The panelists have been asked to assess the bloom intensity on a intensity scale from 0 to 5 (0: not perceivable 1: very weak 2: weak 3: medium 4: strong 5: very strong), resulting in a bloom intensity of 3.7.