Tetrahydrofuran → (E)-(4-bromo-1,6,7,8-tetrahydro-2H-indeno[5,4-b]furan-8-ylidene)acetonitrile

HRID 324610Notes

Reaction equation

HRID 324610 reaction equation
[H-].[Na+].O1CCCC1.[C:8]([CH2:10]P(=O)(OCC)OCC)#[N:9].[Br:19][C:20]1[C:28]2[O:29][CH2:30][CH2:31][C:27]=2[C:26]2[C:25](=O)[CH2:24][CH2:23][C:22]=2[CH:21]=1>O>[Br:19][C:20]1[C:28]2[O:29][CH2:30][CH2:31][C:27]=2[C:26]2/[C:25](=[CH:10]/[C:8]#[N:9])/[CH2:24][CH2:23][C:22]=2[CH:21]=1

Participants

6

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 24758Sodium hydrideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 220047904-bromo-1,2,6,7-tetrahydro-8H-indeno[5,4-b]furan-8-one

Product 1

HCID 68423466(E)-(4-bromo-1,6,7,8-tetrahydro-2H-indeno[5,4-b]furan-8-ylidene)acetonitrileYield 43.1%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

60% Sodium hydride (0.17 g, 4.35 mmols) was added to a tetrahydrofuran (20 ml) solution of diethyl cyanomethylphosphonate (0.77 g, 4.35 mmols) while cooling with ice, and the mixture was stirred for 20 minutes. To this was added a tetrahydrofuran (10 ml) solution of 4-bromo-1,2,6,7-tetrahydro-8H-indeno[5,4-b]furan-8-one (1.00 g, 3.95 mmols), and the mixture was stirred at room temperature further for 2 hours. Water was added to the reaction mixture, which was then extracted with ethyl acetate. The extract was washed with a saturated saline solution, then dried with anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified through silica-gel column chromatography (hexane/ethyl acetate=from 85/15 to 8/2) and then recrystallized from ethyl acetate/isopropyl ether to obtain 0.47 g (yield: 43%) of the target compound.

Workup

  1. temperaturewhile cooling with ice
  2. stirringthe mixture was stirred at room temperature further for 2 hours
  3. extractionwas then extracted with ethyl acetate
  4. washThe extract was washed with a saturated saline solution
  5. dry with materialdried with anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified through silica-gel column chromatography (hexane/ethyl acetate=from 85/15 to 8/2)
  8. customrecrystallized from ethyl acetate/isopropyl ether

Sources & evidence

ORD record
ord-4fc28b76b2f84f54a20bde177374386c
Source dataset
uspto-grants-2001_04
Patent number
US06218429B1

Reaction notes

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