Bis(2-bromoethyl) ether → 6-Bromo-2',3',5',6'-tetrahydrospiro[indene-2,4'-pyran]-1(3H)-one

HRID 1965033Notes

Reaction equation

HRID 1965033 reaction equation
CC(C)([O-])C.[K+].[Br:7][C:8]1[CH:16]=[C:15]2[C:11]([CH2:12][CH2:13][C:14]2=[O:17])=[CH:10][CH:9]=1.Br[CH2:19][CH2:20][O:21][CH2:22][CH2:23]Br>CC(O)(C)C.CC1CCCO1>[Br:7][C:8]1[CH:16]=[C:15]2[C:11]([CH2:12][C:13]3([C:14]2=[O:17])[CH2:23][CH2:22][O:21][CH2:20][CH2:19]3)=[CH:10][CH:9]=1

Participants

6

Reactant 3

HCID 21521Bis(2-bromoethyl) etherHCID 1397781-Indanone, 6-bromo-HCID 23665647Potassium tert-butoxide2×

Product 1

HCID 581981056-Bromo-2',3',5',6'-tetrahydrospiro[indene-2,4'-pyran]-1(3H)-oneYield 24.2%

Reagents, catalysts & solvents 2

HCID 6386tert-ButanolSolventHCID 73012-MethyltetrahydrofuranSolvent

Procedure

A solution of potassium tert-butoxide (3.94 g, 35.1 mmol) in t-BuOH (35 mL) was added dropwise over 15 min to a solution of 6-bromo-1-indanone (3.53 g, 16.73 mmol) in 2-methyl-tetrahydrofuran (350 mL) at r.t. under a nitrogen atmosphere. After 15 min bis(2-bromoethyl)ether (2.102 mL, 16.73 mmol) was added and the resulting mixture was stirred at r.t. for 5 h. Potassium tert-butoxide (0.938 g, 8.36 mmol) was added and the mixture was stirred at r.t. overnight. The mixture was quenched with saturated aq. NH4Cl (150 mL) and the organic layer was separated. The aqueous layer was extracted with EtOAc (3×50 mL) and Et2O (50 mL). The combined organics were washed with brine (100 mL), dried over MgSO4, filtered and concentrated. The resulting residue was taken up in DCM, concentrated onto silica gel and purified on a silica gel column eluted with 0-40% EtOAc in heptane to give 1.14 g (24% yield) of the title compound; MS (ES+) m/z 281 [M+H]1.

Workup

  1. stirringthe mixture was stirred at r.t. overnight
  2. customThe mixture was quenched with saturated aq. NH4Cl (150 mL)
  3. customthe organic layer was separated
  4. extractionThe aqueous layer was extracted with EtOAc (3×50 mL) and Et2O (50 mL)
  5. washThe combined organics were washed with brine (100 mL)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. concentrationconcentrated onto silica gel
  10. custompurified on a silica gel column
  11. washeluted with 0-40% EtOAc in heptane

Sources & evidence

ORD record
ord-2ff221fa98834a9093087a8ab69f5785
Source dataset
uspto-grants-2013_04
Patent number
US08415483B2

Reaction notes

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