Benzaldehyde → HCID 14927900, compound

HRID 913260Notes

Reaction equation

HRID 913260 reaction equation
C([Mg]Cl)(C)C.[CH2:6]([SnH:10]([CH2:15][CH2:16][CH2:17][CH3:18])[CH2:11][CH2:12][CH2:13][CH3:14])[CH2:7][CH2:8][CH3:9].[CH:19](=[O:26])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>C(OCC)C>[Sn:10]([CH:19]([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[OH:26])([CH2:6][CH2:7][CH2:8][CH3:9])([CH2:11][CH2:12][CH2:13][CH3:14])[CH2:15][CH2:16][CH2:17][CH3:18]

Participants

5

Reactant 3

HCID 240BenzaldehydeHCID 5948TributylstannaneHCID 178418918HCID 178418918, compound

Product 1

HCID 14927900HCID 14927900, compoundYield 28.9%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

Under nitrogen, a dry 250 mL round bottom flask was charged with 2.0 M isopropyl magnesium chloride in diethyl ether (20.6 mL, 41.2 mmol) and an additional 15 mL of diethyl ether added. To this stirred solution was added tributyltin hydride (10.0 g, 34.4 mmol) dropwise over a period of 10-15 min. The resulting reaction mixture was heated to reflux, stirred for 1 h, and then cooled down to 0° C. Benzaldehyde (4.0 g, 37.8 mmol) was then added dropwise over a period of approximately 10 min while maintaining the temperature at 0° C. The resulting reaction mixture was then heated to reflux and stirred for 1 h before cooling back down to room temperature. The reaction was then quenched by addition of approximately 15 mL aqueous ammonium chloride under nitrogen. The resulting mixture was filtered through a glass frit and the solids extracted with diethyl ether. The combined organic extracts were concentrated under vacuum and filtered through Florisil. The Florisil pad was washed further with hexane. The combined organic extracts were concentrated under vacuum to afford an oil. Chromatography on silica gel using 95/5 hexane/ethyl acetate as the eluent afforded 3.95 g of Bu3SnCH(OH)Ph as a pale yellow oil. 1H NMR (CDCl3) δ 7.2 (t, 2H, Hmeta), 7.1 d (d, 12H, Hortho), 7.0 (t, 1H, Hpara), 5.1 [d, 1H, CH(OH)], 1.7 [d, 1H, CH(OH)], 1.4-0.7 (m, 27H, Bu's); 119Sn NMR (CDCl3) δ-25.0 relative to SnMe4; 13C NMR (CDCl3) δ 147.8 (Cipso), 128.4 (Cortho or Cmeta), 124.6 (Cpara), 122.9 Cortho or Cmeta), 71.3 [CH(OH)], 28.9 and 27.4 (CH2's), 13.6 (CH3), 9.1 (CH2).

Workup

  1. customThe resulting reaction mixture
  2. temperaturewas heated
  3. temperatureto reflux
  4. temperaturewhile maintaining the temperature at 0° C
  5. customThe resulting reaction mixture
  6. temperaturewas then heated
  7. temperatureto reflux
  8. stirringstirred for 1 h
  9. temperaturebefore cooling back down to room temperature
  10. customThe reaction was then quenched by addition of approximately 15 mL aqueous ammonium chloride under nitrogen
  11. filtrationThe resulting mixture was filtered through a glass frit
  12. extractionthe solids extracted with diethyl ether
  13. concentrationThe combined organic extracts were concentrated under vacuum
  14. filtrationfiltered through Florisil
  15. washThe Florisil pad was washed further with hexane
  16. concentrationThe combined organic extracts were concentrated under vacuum
  17. customto afford an oil

Sources & evidence

ORD record
ord-0d6b295f328f4ea19166ce017d7e5c13
Source dataset
uspto-grants-2011_09
Patent number
US08026333B2

Reaction notes

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