Formaldehyde → HCID 19902683, compound

HRID 2373085Notes

Reaction equation

HRID 2373085 reaction equation
[CH:1]([Si:4]([CH:21]([CH3:23])[CH3:22])([CH:18]([CH3:20])[CH3:19])[CH:5]1[C:17]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[C:11]2[C:6]1=[CH:7][CH:8]=[CH:9][CH:10]=2)([CH3:3])[CH3:2].C([Li])CCC.[CH2:29]=[O:30]>CCOCC.CCCCCC>[CH:21]([Si:4]([CH:1]([CH3:3])[CH3:2])([CH:18]([CH3:20])[CH3:19])[C:5]1([CH2:29][OH:30])[C:6]2[CH:7]=[CH:8][CH:9]=[CH:10][C:11]=2[C:12]2[C:17]1=[CH:16][CH:15]=[CH:14][CH:13]=2)([CH3:23])[CH3:22]

Participants

6

Reactant 3

HCID 712Formaldehyde2×HCID 19902687HCID 19902687, compoundHCID 178418339Butyllithium

Product 1

HCID 19902683HCID 19902683, compoundYield 57.7%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8058HexaneSolvent

Procedure

To a solution of 1.0 g of 9-triisopropylsilylfluorene in 10 mL of dry ether and 30 mL of dry hexane was added dropwise 2.5 mL of 1.5M n-butyllithium. The mixture was refluxed for 15 hours and cooled in an ice bath. Gaseous formaldehyde, generated by heating dried paraformaldehyde at 170° C., was passed through a 8-mm tube into the reaction mixture with the aid of a slow stream of nitrogen until the deep red color had faded to pale yellow (ca. 5 min). The mixture was quenched immediately with 40 mL of half sat'd NH4Cl and washed with brine (10 mL) and water (20 mL). The pooled aqueous layer was extracted with ether (2×20 mL). The combined organic extracts were dried over MgSO4 and the solvent was evaporated in vacuo to give an oil which was chromatographed on silica gel (230-400 mesh, 2×40-cm packed column) with an eluant consisting of Skelly B--ether (3:1), to afford 0.63 g (57.7%) of the alcohol as a white solid. Recrystallization from Skelly F gave 0.38 g (34.8%) of the pure 9-triisopropylsilyl-9-fluorenemethanol as colorless crystals m.p. 106°-107.5° C.; IR (KBr): 3505, 3405 cm-1 (OH); 1H NMR (CDCl3): δ 0.83 (d, 18H, Si-C-Me2), 1.20-1.42 (hept, 3H, C--S--CH), 4.71 (s, 2H, CH2), 7.20-7.95 (m, 8H, aryl).

Workup

  1. temperatureThe mixture was refluxed for 15 hours
  2. temperaturecooled in an ice bath
  3. customhad faded to pale yellow (ca. 5 min)
  4. customThe mixture was quenched immediately with 40 mL of half sat'd NH4Cl
  5. washwashed with brine (10 mL) and water (20 mL)
  6. extractionThe pooled aqueous layer was extracted with ether (2×20 mL)
  7. dry with materialThe combined organic extracts were dried over MgSO4
  8. customthe solvent was evaporated in vacuo
  9. customto give an oil which
  10. customwas chromatographed on silica gel (230-400 mesh, 2×40-cm packed column) with an eluant

Sources & evidence

ORD record
ord-706cf57a4ea54502ac1c745ef8b935b5
Source dataset
uspto-grants-1992_03
Patent number
US05101059

Reaction notes

Loading…