Formic Acid → 2,3,4-Tris(benzyloxy)phenol

HRID 353029Notes

Reaction equation

HRID 353029 reaction equation
OO.[CH:3]([OH:5])=O.[CH2:6]([O:13][C:14]1[C:21]([O:22][CH2:23][C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[C:20]([O:30][CH2:31][C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)C=C[C:15]=1[CH:16]=O)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.Cl>C(Cl)Cl.[O-]S([O-])=O.[Na+].[Na+].C[O-].[Na+]>[CH2:31]([O:30][C:20]1[C:21]([O:22][CH2:23][C:24]2[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=2)=[C:14]([O:13][CH2:6][C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=2)[CH:15]=[CH:16][C:3]=1[OH:5])[C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1

Participants

8

Reactant 4

HCID 284Formic AcidHCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 11122740HCID 11122740, compound

Product 1

HCID 227068882,3,4-Tris(benzyloxy)phenolYield 95%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 24437Sodium SulfiteSolventHCID 10942334Sodium MethoxideSolvent

Conditions

Temperature
0 °C

Procedure

Kolonits, P. et al., Acta Chim Hung. 113:367 (1983). A solution of 30% H2O2 (6 mL, 57.8 mmol) and 85% formic acid (32 mL, 600 mmol) was added dropwise to a solution of 2,3,4-tribenzyloxybenzaldehyde 10 (9.8 g, 23.1 mmol) in CH2Cl2 (50 mL) over 30 min at 0° C. After 1 h of stirring at 0° C., the reaction was stirred at room temperature for 24 h. The reaction was subsequently cooled to 4° C. and diluted with 10% (w/v) aqueous Na2SO3 (50 mL). The aqueous phase was washed with CH2Cl2 (3×40 mL). Drying and: concentration afforded a brown oil which was dissolved in a methanolic solution of NaOMe (30 mL, 0.1 N) and refluxed. After 10 min, the solution was cooled to 4° C. and acidified with 6 N HCl. MeOH was removed in vacuo. The mixture was diluted with H2O (15 mL) followed by extraction of the aqueous phase with benzene (3×40 mL). Drying and concentration afforded 11 (9.0 g, 95%) as a brown oil. 1H NMR (CDCl3): δ7.45-7.31 (m, 15 H), 6.65 (d, J=9 Hz, 1 H), 6.58 (d, J=9 Hz, 1 H), 5.28 (s, 1 H), 5.12 (s, 2 H), 5.11 (s, 2 H), 5.04 (s, 2 H). 13C NMR (CDCl3): δ146.0, 144.0, 142.0, 139.6, 137.3, 137.1, 136.8, 128.4, 128.3 (2), 128.2, 127.9, 127.7, 127.4, 110.4, 109.0, 75.6, 75.3, 71.7. Anal. Calcd for C27H24O4: C, 78.62; H, 5.87. Found: C, 78.71; H, 5.86. HRMS (FAB) calcd for. C27H24O4 (M+H+): 412.1675. Found: 412.1673.

Workup

  1. stirringthe reaction was stirred at room temperature for 24 h
  2. temperatureThe reaction was subsequently cooled to 4° C.
  3. washThe aqueous phase was washed with CH2Cl2 (3×40 mL)
  4. customDrying
  5. concentration: concentration
  6. customafforded a brown oil which
  7. temperaturerefluxed
  8. waitAfter 10 min
  9. temperaturethe solution was cooled to 4° C.
  10. customMeOH was removed in vacuo
  11. additionThe mixture was diluted with H2O (15 mL)
  12. extractionfollowed by extraction of the aqueous phase with benzene (3×40 mL)
  13. customDrying
  14. concentrationconcentration

Sources & evidence

ORD record
ord-3b31c89260fe471489449d3f5b104539
Source dataset
uspto-grants-2004_06
Patent number
US06750049B1

Reaction notes

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