Formaldehyde → 4,4-Bis(hydroxymethyl)-3,4-dihydro-2H-benzo[b]oxepin-5-one

HRID 2265813Notes

Reaction equation

HRID 2265813 reaction equation
[O:1]1[CH2:7][CH2:6][CH2:5][C:4](=[O:8])[C:3]2[CH:9]=[CH:10][CH:11]=[CH:12][C:2]1=2.[C:13](=[O:16])([O-])[O-].[K+].[K+].[CH2:19]=[O:20]>O1CCCC1.O>[OH:20][CH2:19][C:5]1([CH2:13][OH:16])[CH2:6][CH2:7][O:1][C:2]2[CH:12]=[CH:11][CH:10]=[CH:9][C:3]=2[C:4]1=[O:8]

Participants

6

Reactant 3

HCID 712FormaldehydeHCID 11430Potassium CarbonateHCID 3155752,3,4,5-Tetrahydro-1-benzoxepin-5-one

Product 1

HCID 670731254,4-Bis(hydroxymethyl)-3,4-dihydro-2H-benzo[b]oxepin-5-one

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
40 °C

Procedure

To a solution of 3,4-dihydro-2H-benzo[b]oxepin-5-one (12.0 g; 74 mmol) in 215 ml of tetrahydrofuran were added, at room temperature, potassium carbonate (1.01 g) and formalin solution (44 ml; 36% solution in water). The reaction mixture was stirred at 40° C. for 2 days. The mixture was then diluted with 250 ml of water, and the phases were separated and extracted with ethyl acetate. The crude product was purified by column chromatography on silica gel (eluent: 1:1 hexane/ethyl acetate and ethyl acetate). This gave 4,4-bis(hydroxymethyl)-3,4-dihydro-2H-benzo[b]oxepin-5-one (colorless crystals; 13.1 g; 80%).

Workup

  1. customthe phases were separated
  2. extractionextracted with ethyl acetate
  3. customThe crude product was purified by column chromatography on silica gel (eluent: 1:1 hexane/ethyl acetate and ethyl acetate)

Sources & evidence

ORD record
ord-8d1994409ca142d79c7840b7b2957950
Source dataset
uspto-grants-2010_12
Patent number
US07858613B2

Reaction notes

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