p-Diiodobenzene → 8-(4-Iodo-phenyl)-1,4-dioxa-spiro[4.5]decan-8-ol

HRID 1025772Notes

Reaction equation

HRID 1025772 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([I:8])=[CH:4][CH:3]=1.[Li]CCCC.[O:14]1[C:18]2([CH2:23][CH2:22][C:21](=[O:24])[CH2:20][CH2:19]2)[O:17][CH2:16][CH2:15]1>C1COCC1>[I:8][C:5]1[CH:6]=[CH:7][C:2]([C:21]2([OH:24])[CH2:22][CH2:23][C:18]3([O:17][CH2:16][CH2:15][O:14]3)[CH2:19][CH2:20]2)=[CH:3][CH:4]=1

Participants

5

Reactant 3

HCID 12208p-DiiodobenzeneHCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 178418339Butyllithium

Product 1

HCID 578033098-(4-Iodo-phenyl)-1,4-dioxa-spiro[4.5]decan-8-olYield 66.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 1,4-diiodobenzene (16.5 g, 50 mmol) in THF (350 mL) at −78° C. was added n-BuLi (2.5 M, 24 mL) over 1 hour. After being stirred for an additional 30 minutes, a solution of 1,4-dioxa-spiro[4.5]decan-8-one (7.8 g, 50 mmol) in THF (30 mL) was added in and the resulting mixture was stirred for 3 hours. To the mixture was added TMSC1 (5.4 g, 50 mmol) and the resulting mixture was allowed to warm to rt and stirred at rt for 18 hours. The reaction mixture was neutralized to pH 6.0, and extracted with ethyl acetate (3×50 mL). The organic extracts were combined, washed with saline solution (2×50 mL), dried over sodium sulfate, concentrated in vacuo. The residue was chromatographed on silica gel, eluting with hexane/ethyl acetate (95/5 to 100/0). The appropriate fractions were combined to give 8-(4-Iodo-phenyl)-1,4-dioxa-spiro[4.5]decan-8-ol (12 g, 66.6%) with LCMS: 361.2 (M+H+, 100%) and {[8-(4-iodophenyl)-1,4-dioxaspiro[4.5]dec-8-yl]oxy}(trimethyl)silane (6 g, 27%) with LCMS: 433.1 (M+H+, 100%).

Workup

  1. stirringwas stirred for 3 hours
  2. additionTo the mixture was added TMSC1 (5.4 g, 50 mmol)
  3. stirringstirred at rt for 18 hours
  4. extractionextracted with ethyl acetate (3×50 mL)
  5. washwashed with saline solution (2×50 mL)
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated in vacuo
  8. customThe residue was chromatographed on silica gel
  9. washeluting with hexane/ethyl acetate (95/5 to 100/0)

Sources & evidence

ORD record
ord-0c71c70fb8614ac3868d272b406a1360
Source dataset
uspto-grants-2014_05
Patent number
US08729063B2

Reaction notes

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