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

HRID 2367013Notes

Reaction equation

HRID 2367013 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.C[Si](Cl)(C)C>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

6

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 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 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 TMSCl (5.4 g, 50 mmol) and the resulting mixture was allowed to warm to room temperature and stirred at room temperature 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, and 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. stirringstirred at room temperature for 18 hours
  3. extractionextracted with ethyl acetate (3×50 mL)
  4. washwashed with saline solution (2×50 mL)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue was chromatographed on silica gel
  8. washeluting with hexane/ethyl acetate (95/5 to 100/0)

Sources & evidence

ORD record
ord-6769963b2d044ea89ebabd3dbae6c6bd
Source dataset
uspto-grants-2014_04
Patent number
US08697870B2

Reaction notes

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