Formaldehyde → HCID 10712841, compound

HRID 1721465Notes

Reaction equation

HRID 1721465 reaction equation
[C:1]1([C:7]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:8][S:9]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)(=[O:11])=[O:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Li]CCCC.[CH2:29]=[O:30]>C1COCC1>[C:1]1([C:7]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[C:8]([S:9]([C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=2)(=[O:10])=[O:11])[CH2:29][OH:30])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 712Formaldehyde2×HCID 822356HCID 822356, compoundHCID 178418339Butyllithium

Product 1

HCID 10712841HCID 10712841, compoundYield 34%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of 1.25 g (3.90 mmol) of 2,2-diphenyl-1-(phenylsulfonyl) ethene in 20 mL of dry THF at -78° C., was added dropwise under a nitrogen atmosphere 2.8 mL of 1.4M n-BuLi (3.90 mmol). The dark black solution was stirred at -78° C. for 30 minutes. Gaseous fomaldehyde, generated by heating paraformaldehyde at 170° C., was passed through a 5-mm tube into the reaction mixture with the aid of a slow stream of nitrogen at -78° C. for 30 minutes. The mixture was allowed to come to room temperature over a period of 30 minutes while continuing to pass formaldehyde through the reaction mixture until a pale yellow color was observed. The mixture was stirred overnight at room temperature. The mixture was quenched with 50 mL of 5% HCl, and extracted with three 25-mL portions of CH2Cl2. The organic layer was dried over MgSO4, filtered, and the solvent removed in vacuo from a water bath at 45° C. The resulting crude oil was flash chromatographed on silica gel (230-400 mesh, 5×16-cm column) with 30% ether/Skelly B as eluant to give 0.47 g (34%) of the colorless alcohol. In a melting point capillary the compound does not melt but decomposes above 290° C. with blackening; IR (KBr) cm-1 3480, 3040, 1590, 1480, 1440, 1370, 1280, 1130, 1020, 960, 790, 730, 700, 680, 610; 1H NMR (CDCl3) δ 3.47 (t, 1H, OH), 4.61 (d, 2H, CH2O), 6.75-7.58 (m, 15H, phenyl).

Workup

  1. waitwas passed through a 5-mm tube into the reaction mixture with the aid of a slow stream of nitrogen at -78° C. for 30 minutes
  2. waitto come to room temperature over a period of 30 minutes
  3. stirringThe mixture was stirred overnight at room temperature
  4. customThe mixture was quenched with 50 mL of 5% HCl
  5. extractionextracted with three 25-mL portions of CH2Cl2
  6. dry with materialThe organic layer was dried over MgSO4
  7. filtrationfiltered
  8. customthe solvent removed in vacuo from a water bath at 45° C
  9. customchromatographed on silica gel (230-400 mesh, 5×16-cm column) with 30% ether/Skelly B as eluant

Sources & evidence

ORD record
ord-a4a8dda34000492492c4db23e07f997e
Source dataset
uspto-grants-1996_04
Patent number
US05510491

Reaction notes

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