Sodium Hydroxide → Tert-butyl 7-hydroxy-3,4,4a,9a-tetrahydro[1]benzofuro[2,3-c]pyridine-2(1H)-carboxylate

HRID 1616902Notes

Reaction equation

HRID 1616902 reaction equation
B(Br)(Br)Br.C[O:6][C:7]1[CH:12]=[CH:11][C:10]2[CH:13]3[CH2:18][CH2:17][N:16]([C:19]([O:21][C:22]([CH3:25])([CH3:24])[CH3:23])=[O:20])[CH2:15][CH:14]3[O:26][C:9]=2[CH:8]=1.[OH-].[Na+].C(OC(OC(C)(C)C)=O)(OC(C)(C)C)=O>C(Cl)Cl.O>[OH:6][C:7]1[CH:12]=[CH:11][C:10]2[CH:13]3[CH2:18][CH2:17][N:16]([C:19]([O:21][C:22]([CH3:24])([CH3:23])[CH3:25])=[O:20])[CH2:15][CH:14]3[O:26][C:9]=2[CH:8]=1

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 25134Boron tribromideHCID 90495Di-tert-butyl dicarbonateHCID 67324335tert-butyl 7-methoxy-3,4,4a,9a-tetrahydro[1]benzofuro[2,3-c]pyridine-2(1H)-carboxylate

Product 1

HCID 67325270Tert-butyl 7-hydroxy-3,4,4a,9a-tetrahydro[1]benzofuro[2,3-c]pyridine-2(1H)-carboxylateYield 230.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent2×

Procedure

Boron tribromide (285 mL, 1 M, 0.285 mol) in DCM was added over 45 min to a solution of tert-butyl 7-methoxy-3,4,4a,9a-tetrahydro[1]benzofuro[2,3-c]pyridine-2(1H)-carboxylate (33.3 g, 0.11 mol) in DCM (1.2 L). The reaction mixture was kept at 5-8° C. using a water bath cooling. After 1 h stirring, H2O (250 mL) and NaOH (350 mL, 3 M) were added, followed by di-tert-butyl dicarbonate (59.6 g, 0.27 mol). After 16 h stirring, the layers were separated, the organic layer was washed with 0.3 N HCl and H2O, and concentrated. Crystallization using heptane and drying under house vacuum (h.v.) afforded 74 g of expected product. MS m/z 292 [M+H]+

Workup

  1. customwas kept at 5-8° C.
  2. temperaturecooling
  3. stirringAfter 16 h stirring
  4. customthe layers were separated
  5. washthe organic layer was washed with 0.3 N HCl and H2O
  6. concentrationconcentrated
  7. customCrystallization
  8. customdrying under house vacuum (h.v.)

Sources & evidence

ORD record
ord-dec79c38c65445d888865130bcf7f75a
Source dataset
uspto-grants-2014_07
Patent number
US08765779B2

Reaction notes

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