Ethylene Glycol → 1,4-Dioxaspiro[4.5]decane, 8-[4-(3,4-difluorophenyl)-3-cyclohexen-1-yl]-

HRID 2081521Notes

Reaction equation

HRID 2081521 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([C:9]2(O)[CH2:14][CH2:13][CH:12]([CH:15]3[CH2:24][CH2:23][C:18]4([O:22][CH2:21][CH2:20][O:19]4)[CH2:17][CH2:16]3)[CH2:11][CH2:10]2)[CH:5]=[CH:6][C:7]=1[F:8].C(O)CO.C[Si](O[Si](C)(C)C)(C)C.[O-2].[Al+3].[O-2].[O-2].[Al+3]>C(Cl)CCl>[F:1][C:2]1[CH:3]=[C:4]([C:9]2[CH2:14][CH2:13][CH:12]([CH:15]3[CH2:24][CH2:23][C:18]4([O:19][CH2:20][CH2:21][O:22]4)[CH2:17][CH2:16]3)[CH2:11][CH:10]=2)[CH:5]=[CH:6][C:7]=1[F:8]

Participants

6

Reactant 4

HCID 174Ethylene GlycolHCID 24764HexamethyldisiloxaneHCID 9989226AluminaHCID 190011474-[4-Hydroxy-4-(3,4-difluorophenyl)cyclohexyl]cyclohexanone ethyleneacetal

Product 1

HCID 115590611,4-Dioxaspiro[4.5]decane, 8-[4-(3,4-difluorophenyl)-3-cyclohexen-1-yl]-Yield 66.2%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A mixture of 7.8 g of crude 1-(3,4-difluorophenyl)-4-(1,4-dioxa-8-spiro[4.5]decyl) cyclohexanol, 1.05 ml of ethylene glycol, 1.05 g of Amberlyst® 15 (strongly acid ion exchange resin, Fluka AG) and 80 ml of ethylene chloride was refluxed through neutral aluminum oxide for 3 hours. Subsequently, the mixture was cooled to room temperature and washed twice with water. The aqueous phases were extracted twice with methylene chloride. The organic phases where dried over sodium sulfate, filtered and concentrated. Chromatographic purification of the residue on silica gel with hexane/ethyl acetate (vol. 96:4) gave 4,9 g of 8-[4-(3,4-difluorophenyl)-3-cyclohexenyl]-1,4-dioxaspiro [4.5]decane as colorless crystals.

Workup

  1. washwashed twice with water
  2. extractionThe aqueous phases were extracted twice with methylene chloride
  3. dry with materialThe organic phases where dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customChromatographic purification of the residue on silica gel with hexane/ethyl acetate (vol. 96:4)

Sources & evidence

ORD record
ord-5f710469012a4e4f8fa2477df165a849
Source dataset
uspto-grants-1993_02
Patent number
US05185098

Reaction notes

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