Tetrahydrofuran → HCID 86724288, compound

HRID 873740Notes

Reaction equation

HRID 873740 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][CH:14]=1)[O:11][CH2:10][C:6]1([CH2:9][O:8][CH2:7]1)[C:5]2=O.[OH-].[Na+].[CH2:18]1COCC1>[CH3-].C[Al+]C.[CH-]1C=CC=C1.[CH-]1C=CC=C1.[Cl-].[Ti+3]>[Br:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][CH:14]=1)[O:11][CH2:10][C:6]1([CH2:9][O:8][CH2:7]1)[C:5]2=[CH2:18]

Participants

5

Reactant 3

HCID 8028TetrahydrofuranHCID 14798Sodium HydroxideHCID 86724289HCID 86724289, compound

Product 1

HCID 86724288HCID 86724288, compound

Reagents, catalysts & solvents 1

HCID 53384502mu-Chlorobis(eta5-cyclopentadienyl)(dimethylaluminum)-mu-methylenetitaniumCatalyst

Procedure

To a solution of 6-bromo-4H-spiro[chromene-3,3′-oxetan]-4-one (143 mg, 0.531 mmol) in THF (2 mL) was added Tebbe reagent ((C5H5)2TiCH2ClAl(CH3)2, μ-Chloro[di(cyclopenta-2,4-dien-1-yl)]dimethyl(μ-methylene)titaniumaluminum, 0.5 M in toluene, 2 mL) under ice-water bath cooling. After the reaction mixture was stirred at the same temperature for 2 hours and then room temperature for 4 hours, 1M aqueous NaOH (1 mL) was added. After dilution with water and filtration with Celite, the insoluble material was washed with CHCl3. The aqueous phase was extracted with CHCl3 and combined organic layer was concentrated in vacuo. The residue was purified with silica-gel column chromatography to give 6-bromo-4-methylene-4H-spiro[chromene-3,3′-oxetane] (0.10 g).

Workup

  1. temperaturecooling
  2. waitroom temperature for 4 hours
  3. filtrationAfter dilution with water and filtration with Celite
  4. washthe insoluble material was washed with CHCl3
  5. extractionThe aqueous phase was extracted with CHCl3 and combined organic layer
  6. concentrationwas concentrated in vacuo
  7. customThe residue was purified with silica-gel column chromatography

Sources & evidence

ORD record
ord-bca5c25ab73c4dfe996fb61fc87be6d5
Source dataset
uspto-grants-2015_03
Patent number
US08975415B2

Reaction notes

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