Trimethylamine → 4-(((tert-Butyl(dimethyl)silyl)oxy)methyl)benzaldehyde

HRID 2255844Notes

Reaction equation

HRID 2255844 reaction equation
C(Cl)(=O)C(Cl)=O.[Si:7]([O:14][CH2:15][C:16]1[CH:23]=[CH:22][C:19]([CH2:20][OH:21])=[CH:18][CH:17]=1)([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8].CN(C)C.C(=O)(O)[O-].[Na+]>ClCCl.CS(C)=O>[Si:7]([O:14][CH2:15][C:16]1[CH:23]=[CH:22][C:19]([CH:20]=[O:21])=[CH:18][CH:17]=1)([C:10]([CH3:13])([CH3:12])[CH3:11])([CH3:9])[CH3:8]

Participants

7

Reactant 4

HCID 1146TrimethylamineHCID 65578Oxalyl chlorideHCID 516892Sodium BicarbonateHCID 10800836Benzenemethanol, 4-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-

Product 1

HCID 108687284-(((tert-Butyl(dimethyl)silyl)oxy)methyl)benzaldehydeYield 82.2%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of oxalyichloride (1.6 ml) in dry dichloromethane (37 ml) was cooled to -70° C. under N2. Dry dimethylsulfoxide (2.5 ml) in dichloromethane (10 ml) and a solution of 4-(tert-butyldimethylsilyloxymethyl)benzylalcohol (24) (3.94 g, 15.6 mmol) in dichloromethane (20 ml) were added carefully. The reaction mixture was stirred at -70° C. for 1 h. trimethylamine (12 ml) was then added. The reaction mixture was allowed to warm up no 0° C. Saturated aqueous sodium bicarbonate (50 ml) was added, the organic layer was separated and the aqueous layer was extracted with dichloromethane (4×50 ml). The combined organic extracts were dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography over silica (dichloromethane/hexane; 4:1) to yield 4-butyldimethylsilyloxymethyl)benzaldehyde (25) 3.21 g, 82%); νmax /cm-1 2020s, 2850s, 2730w, 1700s, 1090s; δH (CDCl3) 0.11 (6H, s, SiCH3), 0.94 (9 H, s, tert-butyl), 4.80 (2 H, s, CH2O), 7.47 and 7.84 (4 H, AA'BB', PhH) and 9.98 (1 H, s, CHO); (CDCl3) -5.3, 18.4, 25.9, 64.4, 126.2, 129.8, 135.3, 148.6 and 192.0; m/z 251.1467 M+ +H).

Workup

  1. additionwas then added
  2. customthe organic layer was separated
  3. extractionthe aqueous layer was extracted with dichloromethane (4×50 ml)
  4. dry with materialThe combined organic extracts were dried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by column chromatography over silica (dichloromethane/hexane; 4:1)

Sources & evidence

ORD record
ord-2d31521711494cf9adcb10c511692eb1
Source dataset
uspto-grants-1997_08
Patent number
US05653914

Reaction notes

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