Derivatives of 2,2,6-trimethylcyclohexane-carboxylate
A kind of technology of C2-C8, alkynyl group, is used in the composition field that comprises this kind of compound
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Embodiment 1a
[0071] Example 1a: (1R,6S)-2,2,6-trimethylcyclohexanecarbonyl chloride ("acidified chloride intermediate Synthesis of (1R,6S)-isomers"):
[0072]
[0073] Thionyl chloride (1.2 equiv) was added dropwise to (1R,6S)-2,2,6-trimethylcyclohexanecarboxylic acid (1 equiv) in dichloromethane (200 mL) at 0 °C over 15 minutes cold solution. After the addition, the reaction mixture was warmed to room temperature and then heated to 50 °C for 1.5 hours. The mixture was cooled to room temperature and concentrated under reduced vacuum. The ingredients were immediately carried on to the next step.
Embodiment 1b
[0074] Example 1b: (1S,6R)-2,2,6-trimethylcyclohexanecarbonyl chloride ("acidified chloride intermediate Synthesis of (1S,6R)-isomers"):
[0075]
[0076] Thionyl chloride (1.2 equiv) was added dropwise to (1R,6S)-2,2,6-trimethylcyclohexanecarboxylic acid (1 equiv) in dichloromethane (200 mL) at 0 °C over 15 minutes cold solution. After the addition, the reaction mixture was warmed to room temperature and then heated to 50 °C for 1.5 hours. The mixture was cooled to room temperature and concentrated under reduced vacuum. The ingredients were immediately carried on to the next step.
Embodiment 2
[0077] Example 2: Synthesis of (1R,6S)-allyl-2,2,6-trimethylcyclohexanecarboxylate:
[0078]
[0079] Allyl chloride (10.5 equiv; used as solvent) was added dropwise over 20 minutes to the cold flask containing the (1R,6S)-isomer of the acidified chloride intermediate at 0°C. After the addition, the mixture was heated to 75° C. and left overnight (GC showed ~98% purity of the original reaction). The material was diluted with ethyl acetate and washed with 5% Na 2 CO 3 (2×) and water (2×). The aqueous layer was back extracted with ethyl acetate (1x). Combine organics with MgSO 4 Dry, filter and concentrate under reduced pressure. The starting material was purified (yield 67.9%) via fractional distillation (water bath = 70-71 °C, bulb temperature = 56-60 °C, vacuum pressure = 0.18-0.9 Torr). 1 HNMR (400MHz, CDCl 3 ) δppm 0.88 (m, 10H) 1.15 (m, 1H) 1.45 (m, 3H) 1.70 (dd, 1H) 1.83 (m, 2H) 4.55 (m, 2H) 5.21 (d, 1H) 5.32 (m, 1H) ) 5.91 (qd, 1H). 13 CNMR (101MHz, CDCl 3...
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