Sodium hydride → ((4'-Chlorobiphenyl-2-yl)methylene)-1,4dioxaspiro[4.5]decane

HRID 2406243Notes

Reaction equation

HRID 2406243 reaction equation
[H-].[Na+].[I-].[Cl:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[CH2:17][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=[CH:7][CH:6]=1.[CH2:37]1[O:47][C:40]2([CH2:45][CH2:44][C:43](=O)[CH2:42][CH2:41]2)[O:39][CH2:38]1.OS([O-])(=O)=O.[Na+]>CS(C)=O>[Cl:4][C:5]1[CH:6]=[CH:7][C:8]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[CH:17]=[C:38]2[CH2:37][O:47][C:40]3([CH2:45][CH2:44][CH2:43][CH2:42][CH2:41]3)[O:39]2)=[CH:9][CH:10]=1

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 516919Sodium BisulfateHCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 86667196((4'-Chlorobiphenyl-2-yl)methyl)triphenylphosphonium iodide

Product 1

HCID 67054337((4'-Chlorobiphenyl-2-yl)methylene)-1,4dioxaspiro[4.5]decaneYield 52%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
80 °C

Procedure

A suspension of sodium hydride (60% in mineral oil, 77 mg, 1.92 mmol) in DMSO (5.8 mL) was heated for 1 hour at 80° C. and then cooled to rt. ((4′-Chlorobiphenyl-2-yl)methyl)triphenylphosphonium iodide (1.04 g, 1.76 mmol) was added to the suspension and then, after stirring 10 minutes at room temperature, 1,4-cyclohexanedione monoethylene acetal (0.25 g, 1.60 mmol) was added. The reaction mixture was heated at 80° C. for 3 hours. After standing at rt overnight, the reaction mixture was poured into a saturated solution of NaHSO4 and extracted with EtOAc. The organic layers were combined, washed with brine, dried with Na2SO4, filtered and concentrated. The crude was purified by flash chromatography (silica gel, 0% to 30% EtOAc in heptane) to give ((4′-Chlorobiphenyl-2-yl)methylene)-1,4dioxaspiro[4.5]decane (0.28 g, 52%) as a white solid: 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 7.12-7.33 (m, 8 H), 5.98 (s, 1 H), 3.92 (s, 4 H), 2.30-2.36 (m, 2 H), 2.22-2.29 (m, 2 H), 1.62-1.71 (m, 2 H), 1.52-1.58 (m, 2 H).

Workup

  1. temperaturecooled to rt
  2. temperatureThe reaction mixture was heated at 80° C. for 3 hours
  3. waitAfter standing at rt overnight
  4. extractionextracted with EtOAc
  5. washwashed with brine
  6. dry with materialdried with Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe crude was purified by flash chromatography (silica gel, 0% to 30% EtOAc in heptane)

Sources & evidence

ORD record
ord-f708ae90dd7f4c9d9bd3bbeb83ffd74d
Source dataset
uspto-grants-2014_08
Patent number
US08809352B2

Reaction notes

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