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Substituted cyclohexanones

A cyclic, mandatory technique used in the preparation of organic compounds, compounds of elements of group 4/14 of the periodic table, organic chemistry, etc.

Active Publication Date: 2008-07-16
FIRMENICH SA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In WO05 / 077875 its inventors describe a process for the preparation of similar cyclohexenones, but this prior art process requires the use of diketones instead of compounds of formula (I)
[0006] Snider et al. (J.Org.Chem., 1991, 4908), Agami et al. (Bull.Soc.Chim.Fr., 1987, 358) or Fehr et al. (Eur.J.Org.Chem., 2004, 1953) also describe Additional methods for the preparation of similar cyclohexenones have been proposed, but these methods imply the use of different starting materials as well as different reagents

Method used

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  • Substituted cyclohexanones

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0142] Preparation of (-)-(1R,11S,14R)-1-Hydroxy-14-methyl-bicyclo[9.4.0]pentadecane-12- Ketone (13) and (-)-(1R,11R,14R)-1-hydroxy-14-methyl-bicyclo[9.4.0]pentadecane-12- Ketones (14)

[0143] Catalyst preparation: CH with TiCl4 (9.50g (5.52ml); 50mmol) 2 Cl 2 (50ml) (temperature 30~40 ℃) solution handles the CH of freshly distilled (+)-N-isopropylephedrine (10.35g, 50.0mmol) within 5 minutes 2 Cl 2 (150ml) solution. After joining, at N 2 The solvent was distilled down. The residue was dried under vacuum (0.01 mbar): 21.77 g.

[0144] Aldol reaction: The catalyst obtained above (20.71 g; max. 47.6 mmol; 0.80 equivalents) was poured into a 250 ml container containing NMP (57 ml) while stirring. The temperature was brought to 34°C. After 5 minutes, solid 3-methyl-1,5-cyclopentadecanedione (15) (14.98 g, 59.4 mmol) was added to the stirred dark brown solution. After 5 minutes, use H 2 O (89.1 mg; 4.95 mmol) of TMEDA (6.67 g, 8.54 ml, 57.5 mmol) and the solution wa...

Embodiment 2

[0156] Preparation of (1RS, 11RS, 14RS)-1-hydroxy-14-methyl-bicyclo[9.4.0]pentadecane-12- Ketones (16)

[0157] with ZrCl 3 A solution of OPr (36%, in AcOEt) (65.25g, 91.6mmol) was treated with CH 2 Cl 2 (210ml) solution. After 5 minutes, use NBu 3 (19.43g, 25.0ml, 105mmol) the light yellow solution was treated at -10~0°C. After 15 minutes, the reaction mixture was poured into water and extracted with ether. Washing (H 2 O, saturated NaHCO 3 , NaCl), dry (Na 2 SO 4 ) and evaporate the organic phase. Crystallization from heptane (345ml) yielded 11.93g of (16) (yield: 79%) and 2.80g of mother liquor, from which an additional 1.39g (yield: 9%) of (16) was recovered. The spectrum is the same as that of (14).

Embodiment 3

[0159] Preparation of (+)-(S)-14-methylbicyclo[9.4.0]pentadeca-1(11)-en-12-one (17)

[0160] use me 3 N·HCl (1.89 g; 19.80 mmol) treatment of (13) / (14) (9.97 g; 39.56 mmol) (obtained by repeating Example 1 after one chromatography) 2 Cl 2 (300ml) solution. At -15°C, with NEt 3 (15.98 g, 158.2 mmol) and the stirred mixture was continuously treated dropwise with MsCl (13.58 g, 118.7 mmol). The reaction mixture was stirred at 0°C for 1 hour and at 25°C for 15 hours. It was then poured into 5% HCl and extracted with ether. Washing (H 2 O, saturated NaHCO 3 , NaCl), dry (Na 2 SO 4 ) and evaporation of the organic phase gave a crude oil. The oil was heated at 80°C in toluene (60ml) and DBU (9.02g, 59.34mmol) for 1 hour, cooled and purified etc. as described above (5% HCl and extraction). Bulb-to-bulb distillation (oven temperature 100-150° C. / 0.01 mb) afforded 8.72 g (yield: 94%) of (17) (29% ee).

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PUM

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Abstract

The present invention relates to a cyclohexanone derivative of formula (I) in the form of any one of its isomers or mixture thereof. The invention concerns also the preparation and the use of said derivative. The invention's compound is a useful starting material for the preparation of various optically active compounds.

Description

technical field [0001] The present invention relates to the field of organic synthesis, in particular it relates to cyclohexanone derivatives of formula (I) in the form of any one isomer or a mixture thereof and as defined below, [0002] [0003] The invention also relates to the preparation of said derivatives and their use as raw materials. Background technique [0004] To the best of our knowledge, the cyclohexanone derivatives of formula (I) are novel compounds. Furthermore, no method has been found in the prior art that enables the preparation of analogs of cyclohexanone (ie, compounds having a hydroxyl derivative at the 3-position and a hydrocarbon derivative at the 5-position) of the present invention. [0005] The cyclohexanone derivatives of formula (I) are useful starting materials for the preparation of the corresponding cyclohexenones. In WO05 / 077875 its inventors describe a process for the preparation of similar cyclohexenones, but this prior art process r...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/603C07C49/517C07C49/497C07C49/513C07C49/623C07F7/18C07C45/65C07C45/66
CPCC07C49/497C07B2200/07C07C49/753C07C49/513C07C49/04C07C49/623C07C49/517C07C45/004C07C49/603C07F7/1852C07F7/1804
Inventor 奥利弗·克诺普夫查尔斯·费尔何塞·加林多
Owner FIRMENICH SA
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