Citric Acid → 1-[5-(Tetrahydro-pyran-2-yloxymethyl)-furan-2-yl]-ethanol

HRID 2040044

Reaction equation

[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]1[O:13][C:12]([CH:14]=[O:15])=[CH:11][CH:10]=1.[CH3:16][Mg]Cl.O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>C1COCC1.CC(OC)(C)C>[O:1]1[CH2:6][CH2:5][CH2:4][CH2:3][CH:2]1[O:7][CH2:8][C:9]1[O:13][C:12]([CH:14]([OH:15])[CH3:16])=[CH:11][CH:10]=1

Participants

Conditions

Temperature: 1 °C

Procedure

Crude 5-(tetrahydro-pyran-2-yloxymethyl)-furan-2-carbaldehyde (171 g) was dissolved in THF (1 L) and cooled to 1° C. Methylmagnesium chloride (3 M in THF, 325 mL, 0.97 mol) was then added while keeping the internal temperature below 5° C. After the addition, the reaction mixture was stirred at rt for 1 h. Water (1 L), TBME (1 L) and 40% aq. citric acid (200 mL) were added, the layers separated and the org. layer washed with water (500 mL) and evaporated to dryness to give 174 g of crude 1-[5-(tetrahydro-pyran-2-yloxymethyl)-furan-2-yl]-ethanol (95% yield). Part of the crude material (96 g, 0.43 mol) was dissolved in CH2Cl2 (1 L) and treated with MnO2 (371 g, 4.26 mol) at rt. The reaction mixture was heated to 45° C. and stirred at this temperature for 24 h. The mixture was then filtered over celite and the filter cake washed with CH2Cl2. The filtrate was evaporated to dryness to give crude 1-[5-(tetrahydro-pyran-2-yloxymethyl)-furan-2-yl]-ethanone (89 g, 93%) as a yellow oil.

Workup

customthe internal temperature below 5° C
additionAfter the addition
customthe layers separated
washlayer washed with water (500 mL)
customevaporated to dryness

Sources & evidence

ORD record: ord-79cffd202044423b9f56460cec505797
Source dataset: uspto-grants-2013_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08580831B2

Linked notes

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