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(S)-(+)-3-HYDROXY-2,2-DIMETHYLCYCLOHEXANONE

spectroscopy, SYNTHESIS, Uncategorized

Dec 192014

(S)-(+)-3-hydroxy-2,2-dimethylcyclohexanone

bp 85–87°C at 3.7 mm, [α]²¹D + 23.0° (CHCl₃, c 2.0)

The spectral properties of (S)-(+)-3-hydroxy-2,2-dimethylcyclohexanone are as follows:

IR v_max (film) cm⁻¹: 3470 (s), 1705 (s), 1120 (m), 1055 (s), 985 (s), 965 (m);

¹H NMR (250 MHz, CDCl₃) δ: 1.11 (s, 3 H), 1.15 (s, 3 H), 1.60–1.71 (m, 1 H), 1.76–1.86 (m, 1 H), 1.96–2.05 (m, 2 H), 2.16 (br s, 1 H), 2.35–2.45 (m, 2 H), 3.69 (dd, 1 H, J = 7.6, 2.9);

¹³C NMR (76 MHz, CDCl₃) δ: 19.7, 20.7, 22.9, 29.0, 37.3, 51.3, 77.8, 215.3.

The optical purity of (S)-(+)-3-hydroxy-2,2-dimethylcyclohexanone can be determined by HPLC analysis.

The (S)-α-methoxy-α-trifluoromethylphenylacetate (MTPA ester) is prepared according to the reported procedure:³ HPLC analysis (Column, Nucleosil^® 50-5, 25 cm × 4.6 mm; eluant, hexane : THF = 30 : 1, 1.03 mL/min; detected at UV 256 nm) retention time 35.6 min (98.0–99.4%) and 29.6 min (0.6–(2.0%). Therefore, the optical purity is determined to be 96.0–98.8% ee.

Analysis of the MTPA ester of this product by 250 MHz ¹H NMR and capillary GLC (12.5 m, 5% methyl silicone column) failed to detect any more of the minor diastereomer than would have been expected from the purity (98% ee) of the MTPA-Cl employed.

NOTE….Intermediate is

2,2-dimethylcyclohexane-1,3-dione bp 92–97°C (4 mm)

37–38°C.

The spectra are as follows: ¹H NMR (250 MHz, CDCl₃) δ: 1.29 (s, 6 H), 1.93 (5 lines, 2 H, J = 6.5), 2.67 (t, 4 H, J = 6.9); ¹³C NMR (76 MHz, CDCl₃) δ: 18.1, 22.3, 37.4, 61.8, 210.6.

Natural products synthesized from (S)-3-hydroxy-2,2-dimethylcyclohexanone

References and Notes

Department of Agricultural Chemistry, The University of Tokyo, Yayoi 1-1-1, Bunkyo-Ku, Tokyo 113, Japan.
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