Organic compounds

Abstract

The use as fragrance ingredient of 4methylene2(2methylprop1enyl)tetrahydropyran.

Claims

1. A fragrance material comprising 4-methylene-2-(2-methylprop-1-enyl)-tetrahydropyran in combination with nerol oxide at a weight ratio of from 99:1 to 8:2.

2. A fragrance mixture consisting essentially of 4-methylene-2-(2-methylprop-1-enyl)-tetrahydropyran and nerol oxide at a weight ratio of from 99.1 to 8:2.

3. A fragrance application comprising the fragrance material of claim 1, and a consumer product base.

4. The fragrance application of claim 3 wherein the consumer product base is selected from the group consisting of fine perfumery, fabric care, household products and personal care products.

5. A method of improving, enhancing or modifying a consumer product base comprising: adding to the consumer product base an olfactory acceptable amount of 4-methylene-2-(2-methylprop-1-enyl)-tetrahydropyran.

6. The method of claim 5 in which there is additionally present nerol oxide, and the 4-methylene-2-(2-methylprop-1-enyl)-tetrahydropyran and nerol oxide are present in a respective weight ratio of from 99:1 to 8:2.

Description

(1) The disclosure is now further described with reference to the following non-limiting examples.

Example 1: Dehydro Rose Oxide

(2) A round-bottomed flask equipped with a Dean-Stark trap was charged with toluene (60 mL) and an aqueous solution of NaHSO.sub.4 (0.56 mL, 10% in water, 56 mg, 0.2 mol %). The reaction mixture was preheated to reflux (150 C. oilbath), while a 1:1 mixture of neat 3-methylbut-3-en-1-ol (23.5 ml, 232 mmol, 1.0 equiv) and 3-methylbut-2-enal (19.5 g, 232 mmol, 1.0 equiv) was added with a syringe pump (10 mL/h). After refluxing over night, an additional amount of a 10% NaHSO.sub.4 solution (0.5 mL, 56 mg, 0.2 mol %) was added at room temperature to the reaction mixture and refluxing was continued for 4 h. A total amount of 3.5 mL of water was collected in the trap. The reaction mixture was allowed to cool to room temperature and extracted with MTBE, washed with diluted aq. 0.02M NaOH, water and brine, dried over MgSO.sub.4 and filtered. The solvent was removed under reduced pressure. The crude product (33 g) was purified by Kugelrohr distillation (120 C. at 8 mbar) to give a mixture of dehydro rose oxide (DHRO) and nerol oxide (NO) (19.5 g, 55% chemical yield, DHRO/NO 63:25, 88% purity by GC). For the olfactive quality, the product was repurified by fractional distillation over a 10 cm Vigreux column to afford a mixture of dehydro rose oxide (DHRO) and nerol oxide (NO) (10.8 g, 31% olfactive yield, 85:15 DHRO/NO, bp: 55-57 C. at 8 mbar) as a colorless liquid. In addition, a second fraction containing a higher content of nerol oxide NO (3.2 g, 9% yield, DHRO/NO 60:40, bp: 60 C. at 8 mbar) was isolated.

(3) Analytical data for dehydro rose oxide (DHRO):

(4) .sup.1H-NMR (400 MHz, CDCl.sub.3, /ppm): 5.23-5.15 (m, 1H), 4.74-4.67 (m, 2H), 4.04 (ddd, J=1.7, 5.6, 11.0 Hz, 1H), 3.94 (ddd, J=2.7, 8.1, 10.8 Hz, 1H), 3.40 (ddd, J=2.7, 11.0, 12.1 Hz, 1H), 2.35-2.23 (m, 1H), 2.20-2.01 (m, 3H), 1.71 (d, J=1.5 Hz, 3H), 1.66 (d, J=1.5 Hz, 3H). .sup.13C-NMR (101 MHz, CDCl.sub.3, /ppm): 144.5, 136.0, 125.6, 108.3, 75.7, 68.3, 41.2, 34.9, 25.7, 18.3. GC-MS (ESI, m/z): 152 (M.sup.+, 42), 137 (100), 107 (15), 85 (60), 83 (18), 67 (58), 53 (23), 41 (31), 40 (19), 39 (35), 29 (14), 27 (14).

(5) Odor description: green, rosy, rose oxide like, metallic

(6) Analytical data for nerol oxide (NO):

(7) .sup.1H-NMR (400 MHz, CDCl.sub.3, /ppm): 5.42-5.35 (m, 1H), 5.25-5.16 (m, 1H), 4.24-4.11 (m, 3H), 2.09-1.95 (m, 1H), 1.85-1.76 (m, 1H), 1.73 (d, J=1.5 Hz, 3H), 1.70-1.66 (m, 6H). .sup.13C-NMR (101 MHz, CDCl.sub.3, /ppm): 135.9, 131.8, 125.7, 119.6, 70.6, 65.5, 35.9, 25.7, 22.9, 18.3. GC-MS (ESI, m/z (%)): 152 (M.sup.+, 7), 109 (7), 96 (11), 85 (31), 83 (82), 69 (20), 68 (100), 67 (91), 53 (26), 41 (36), 39 (36), 29 (22), 27 (18).

(8) Odor description: green, weedy, cortex, herbal, narcissus, celery

Example 2: Fragrance Formulation

(9) TABLE-US-00001 Parts by weight Ethyl Cyclohexyl Acetate 5 Acetophenone 0.5 Agrumex (2-(tert-butyl)cyclohexyl acetate) 26 Phenyl Ethyl Alcohol (2-phenylethan-1-ol) 110 Hydratropicaldehyde Dimethylacetal (1,1-dimethoxypropan-2- 16 yl)benzene) L-Carvone 4 Citronellol 122 Cyclal C (2,4-dimethylcyclohex-3-ene-1-carbaldehyde) 5 Dihydro Myrcenol 105 Diphenyl Oxide 9 Dipropylene Glycol 11 Estragole (1-allyl-4-methoxybenzene) 10 Gardenol (1-phenylethyl acetate) 12 Hedione (methyl 2-(3-oxo-2-pentylcyclopentyl)acetate) 3 Isopentyrate (4-methylpent-4-en-2-yl isobutyrate) 5 Jasmacyclene (3a,4,5,6,7,7a-hexahydro-1H-4,7- 60 methanoinden-6-yl acetate) Lilial (3-(4-(tert-butyl)phenyl)-2-methylpropanal) 80 Linalool 230 Manzanate (ethyl 2-methylpentanoate) 4 Menthone (2-isopropyl-5-methylcyclohexan-1-one) 12 Peach Pure (5-heptyldihydrofuran-2(3H)-one) 0.5 Rose Oxide 14 Hexyl Salicylate 40 Serenolide (2-(1-(3,3-dimethylcyclohexyl)ethoxy)- 6 2-methylpropyl cyclopropanecarboxylate Terpineol Pure (2-(4-methvlcyclohex-3-en-1-yl)propan-2-ol) 60 Total: 950

(10) The formula was also prepared with the 14 parts of rose oxide being substituted by 14 parts of a 85:15 weight ratio mixture of dehydro rose oxide and nerol oxide, prepared according to Example 1.

(11) The replacement of Rose Oxide resulted in a fragrance formulation described as being more green petitgrain, vegetable-like, and more powerful than the formulation comprising Rose oxide.