1,2-Dimethoxyethane → 8-(4-Fluorophenyl)-1,4-dioxaspiro[4.5]dec-7-ene

HRID 12050Notes

Reaction equation

HRID 12050 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].[F:7][C:8]1[CH:13]=[CH:12][C:11](OB(O)O)=[CH:10][CH:9]=1.[Cl-].[Li+].C[O:21][CH2:22][CH2:23][O:24][CH3:25]>>[F:7][C:8]1[CH:13]=[CH:12][C:11]([C:8]2[CH2:13][CH2:12][C:25]3([O:21][CH2:22][CH2:23][O:24]3)[CH2:10][CH:9]=2)=[CH:10][CH:9]=1

Participants

5

Reactant 4

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 433294Lithium ChlorideHCID 219397714-Fluoro-phenylboric acid

Product 1

HCID 152326828-(4-Fluorophenyl)-1,4-dioxaspiro[4.5]dec-7-ene

Conditions

Temperature
80 °C

Procedure

In an argon-charged flask, 2M sodium carbonate (4.8 mmol), 1,2-dimethoxyethane (8 ml), 4-fluorophenylboric acid (2.8 mmol), lithium chloride (6 mmol), 1,4-dioxaspiro[4.5]dec-7-en-8-yl-trifluormethane-sulphonic acid ester (2 mmol) and tetrakis(triphenyl-phosphine)palladium (0.1 mmol) are combined and stirred overnight at 80° C. The reaction mixture is concentrated in a vacuum and the residue is dispersed in dichloromethane/2M aqueous sodium carbonate solution. The aqueous phase is extracted with dichloromethane. The combined organic phases are then dried over sodium sulphate and the solvent is evaporated off in a vacuum. From the residue, after column chromatography using silica gel (ethyl acetate/heptane 1:4), pure 8-(4-fluorophenyl)-1,4-dioxaspiro[4.5]dec-7-ene is isolated (Synthesis 1993, 735-762): tR 3.61 min (LC-1); ESI-MS(+): m/z 235.34 [M+H]+. 1H NMR (ppm,CDCl3): 7.35 (2H); 6.95 (2H); 5.9 (1H); 4.05 (4H); 2.65 (2H); 2.45 (2H); 1.9 (2H).

Workup

  1. additionIn an argon-charged flask
  2. concentrationThe reaction mixture is concentrated in a vacuum
  3. additionthe residue is dispersed in dichloromethane/2M aqueous sodium carbonate solution
  4. extractionThe aqueous phase is extracted with dichloromethane
  5. dry with materialThe combined organic phases are then dried over sodium sulphate
  6. customthe solvent is evaporated off in a vacuum

Sources & evidence

ORD record
ord-777ab7736df042afb2a421bd409f5134
Source dataset
uspto-grants-2010_06
Patent number
US07727979B2

Reaction notes

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