Water → rel-(1R,6S)-2,2,6-Trimethylcyclohexanecarboxaldehyde

HRID 530233Notes

Reaction equation

C([O:4][CH:5]=[CH:6][C@@H:7]([CH3:14])[CH2:8][CH2:9][CH:10]=[C:11]([CH3:13])[CH3:12])(=O)C.P(=O)(O)(O)O.O>C1(C)C=CC=CC=1>[CH3:13][C:11]1([CH3:12])[CH2:10][CH2:9][CH2:8][C@H:7]([CH3:14])[C@H:6]1[CH:5]=[O:4]

Participants

Conditions

Temperature: 100 °C

Procedure

A solution of crude product of Example 3a (6.36 g, 32.4 mmol) in toluene (11 mL) (15.7 g) was added 85% phosphoric acid (12 mL). The mixture was heated to 100° C. for 4 hours. The reaction mixture was cooled to room temperature and toluene (12 mL) along with water (24 mL) was added and the layers were separated. The aqueous layer was extracted with toluene (12 mL×2). The combined organic layers were washed with saturated aqueous sodium bicarbonate (50 mL×2) and brine (50 mL×2). Concentration and distillation under reduced pressure (b.p. 65-70° C.) afforded the title compound as a 9:1 mixture of epimers as a colorless oil (2.51 g, Yield: 50%). 1H NMR (400 MHz, CDCl3) (Major) δ 9.63 (d, J=5.2 Hz, 1H), 2.03-1.91 (m, 1H), 1.83-1.75 (m, 1H), 1.64-1.60 (m, 1H), 1.54-1.48 (m, 1H), 1.40-1.35 (m, 1H), 1.24-1.14 (m, 1H), 1.02 (s, 3H), 0.97 (s, 3H), 0.95-0.84 (m, 2H), 0.81 (d, J=6.4 Hz, 3H) ppm. [α]D24=+5.20° (c=1.00, dichloromethane).

Workup

temperatureThe reaction mixture was cooled to room temperature
customthe layers were separated
extractionThe aqueous layer was extracted with toluene (12 mL×2)
washThe combined organic layers were washed with saturated aqueous sodium bicarbonate (50 mL×2) and brine (50 mL×2)
concentrationConcentration and distillation under reduced pressure (b.p. 65-70° C.)

Sources & evidence

ORD record: ord-4f5caca31d204fb08a171fd619b4c6bc
Source dataset: uspto-grants-2016_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09353063B2

Reaction notes

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