Methyl iodide → 7-Methyl-1,4-dioxaspiro[4.5]decan-8-one

HRID 1970975Notes

Reaction equation

[Li+].C[Si]([N-][Si](C)(C)C)(C)C.[O:11]1[C:15]2([CH2:20][CH2:19][C:18](=[O:21])[CH2:17][CH2:16]2)[O:14][CH2:13][CH2:12]1.[CH3:22]I.[Cl-].[NH4+]>CN(C=O)C.CC(OC)(C)C>[CH3:22][CH:19]1[C:18](=[O:21])[CH2:17][CH2:16][C:15]2([O:14][CH2:13][CH2:12][O:11]2)[CH2:20]1

Participants

Conditions

Temperature: -60 °C

Procedure

To a stirred solution of LHMDS (1.0 M in THF, 2.1 L, 2.1 mol) at −60° C. was added 1,4-dioxaspiro[4.5]decan-8-one (300 g, 1.9 mol) in DMF (1.2 L) slowly via an addition funnel while maintaining the reaction temperature below −60° C. The reaction mixture was allowed to stir at −60° C. for 1.5 h, and treated with MeI (286 g, 2.0 mol) via an addition funnel. The reaction mixture was allowed to warm to room temperature over 3 h, and treated with half-saturated ammonium chloride solution (2 L). The mixture was diluted with MTBE (2 L), washed with water (×3), dried (magnesium sulfate), and concentrated. The residue was azeotroped with isooctane (500 mL×2), and recrystallized from isooctane to afford the title compound. 1H NMR (400 MHz, CDCl3) δ 4.05-3.95 (m, 4H); 2.70 (m, 1H); 2.61 (dtd, 1H); 2.33 (ddd, 1H); 2.10-1.97 (m, 2H); 1.92 (dt, 1H); 1.68 (t, 1H); 1.00 (d, 3H).

Workup

temperaturewhile maintaining the reaction temperature below −60° C
temperatureto warm to room temperature over 3 h
washwashed with water (×3)
dry with materialdried (magnesium sulfate)
concentrationconcentrated
customThe residue was azeotroped with isooctane (500 mL×2)
customrecrystallized from isooctane

Sources & evidence

ORD record: ord-bf43feb564db4cfca03c48f1e1befdbc
Source dataset: uspto-grants-2013_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08431569B2

Reaction notes

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