1,4-Dioxaspiro[4.5]decan-8-one → HCID 12953626, compound

HRID 1578040Notes

Reaction equation

HRID 1578040 reaction equation
[CH3:1][O:2][CH:3]([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1Br.C([Li])CCC.[O:22]1[C:26]2([CH2:31][CH2:30][C:29](=O)[CH2:28][CH2:27]2)[O:25]C[CH2:23]1>O1CCCC1.CCCCCC.O>[C:4]1([CH:3]2[C:11]3[C:16](=[CH:15][CH:14]=[CH:13][CH:12]=3)[C:1]3([CH2:23][O:22][C:26]4([CH2:31][CH2:30][CH2:29][CH2:28][CH2:27]4)[O:25]3)[O:2]2)[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1

Participants

7

Reactant 3

HCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 12319472HCID 12319472, compoundHCID 178418339Butyllithium

Product 1

HCID 12953626HCID 12953626, compoundYield 39.6%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
-50 °C

Procedure

To a cooled (-50° C.) stirred solution of 27.7 g of 2-bromobenzhydryl methyl ether in 80 ml of dry tetrahydrofuran is added dropwise under nitrogen 60 ml of 2.4 M n-butyllithium in hexane. The mixture is stirred for 2 hours and a solution of 15.9 g of 1,4-dioxaspiro[4.5]decan-8-one in 50 ml of dry tetrahydrofuran is added dropwise, maintaining the temperature at -40° to -30° C. The mixture is stirred overnight at -70° to +10° C., diluted with 100 ml of water and extracted with 100 ml of dichloromethane. The organic phase is washed with water (2×50 ml), dried over anhydrous sodium sulfate and concentrated in vacuo. A solution of the residue in 400 ml of ethanol is stirred with 50 ml of hydrogen bromide/ether at room temperature for 3 hours. The solvent is removed under reduced pressure and the remaining oil crystallizes from 100 ml of methanol to give 39.6% of product, mp: 130°-132° C.

Workup

  1. temperaturemaintaining the temperature at -40° to -30° C
  2. stirringThe mixture is stirred overnight at -70° to +10° C.
  3. extractionextracted with 100 ml of dichloromethane
  4. washThe organic phase is washed with water (2×50 ml)
  5. dry with materialdried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. stirringA solution of the residue in 400 ml of ethanol is stirred with 50 ml of hydrogen bromide/ether at room temperature for 3 hours
  8. customThe solvent is removed under reduced pressure
  9. customthe remaining oil crystallizes from 100 ml of methanol

Sources & evidence

ORD record
ord-7c0505df17ba45ceb5ef2fae9ca6875e
Source dataset
uspto-grants-1981_09
Patent number
US04290958

Reaction notes

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