Optically active ester compounds and application in perfume compositions
A technology of compounds and compositions, applied in the field of optically active ester compounds, capable of solving problems such as unrevealed or proposed chiral centers
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Embodiment I
[0049]
[0050] (3,3-Dimethylcyclohexyl) diethyl malonate Malonic acid
[0051] Ethanol (+ / -)(1RS, 1’RS)-1-(3’, 3’-
[0052] Dimethyl-1'-cyclohexyl)ethyl
[0053] ethyl ester
[0054] Preparation of (+ / -)-(1RS,1'RS)-1-(3',3'-dimethyl-1'-cyclohexyl)ethylethyl malonate:
[0055] Malonate (+ / -)-(1RS, 1'RS)-1-(3', 3'-dimethyl-1'-cyclohexyl)ethane was prepared according to the above method disclosed in U.S. Patent No. 6,774,260 ethyl ethyl ester (Formula II). 250 grams of (3,3-dimethylcyclohexyl) ethanol ( IFF) and 1000 g of diethyl malonate (obtained from Aldrich Chemical Company, Inc., Milwaukee, Wisconsin) was heated to 160° C. while distilling off ethanol . Vacuum distillation provided 405 g of product (Formula II).
[0056] The product has a boiling point of 138°C at 3.5 mm Hg. The NMR analysis of the product is as follows: 0.81-1.66ppm (m, 9H); 0.8...
Embodiment II
[0059]
[0060] (+)-(3S)-3,7-bis(+)(1S,1’R)1-(3,3-dimalonic acid
[0061] Methyl-octyl-1,6-dimethylcyclohexyl)ethanol (+)(1S,1’R)-1-(3’,3’-di
[0062] ene methyl-1'-cyclohexyl) ethyl ethyl
[0063] ester
[0064] Preparation of (+)-(1S,1'R)-1-(3',3'-dimethyl-1'-cyclohexyl)ethylethyl malonate:
[0065] First, according to the method described by Ansari, H.R. (Tetrahedron (1973) 29, 1559-1564), from (+)-(3S)-3,7-dimethyl-octa-1,6-diene (available from IFF purchased) to obtain the chiral alcohol (+)-(1S,1'R)-1-(3',3'-dimethylcyclohexyl)ethanol. Following the procedure detailed in Example I, the resulting chiral alcohol was reacted with diethyl malonate to form malonate (+)-(1S,1'R)-1-(3',3' -Dimethyl-1'-cyclohexyl) ethyl ethyl ester (formula III), whose [α] D 25 Optical rotation = +4.6 (c = 1).
[0066] Chiral GC analysis showed the product to be in an enantiomeric excess of 95% ee.
[0067] The compound i...
Embodiment III
[0069]
[0070] (3,3-Dimethylcyclohexyl 1-(3,3-Dimethylcyclohexyl)-(1S,1’RS)-1-(3’,3’-dimethyl
[0071] base) ethanol ethyl ketone (cyclohexyl) ethanol
[0072]
[0073] Malonate
[0074] (+)-(1S, 1’RS)-1-(3’, 3’-Two
[0075] Methyl-1'-cyclohexyl) ethyl ethyl
[0076] ester
[0077] Preparation of (+)-(1S,1'RS)-1-(3',3'-dimethyl-1'-cyclohexyl)ethylethyl malonate:
[0078] Oxidation of (3,3-dimethylcyclohexyl)ethanol to form 1-(3,3-dimethyl-cyclohexyl)-ethanone ( IFF), the compound was then hydrogenated using an asymmetric hydrogenation catalyst (R)Xyl-P-Phos RuCl2(R, R)-DPEN (as described by Chen et al. (Organic Chemistry (J.Org.Chem.) (2002) 67, 7908- 7910) to form (1S, 1'RS)-1-(3', 3'-dimethylcyclohexyl)ethanol. According to the method...
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