Potassium Carbonate → 2-[2-[[Tert-butyl(dimethyl)silyl]oxymethyl]-3-tert-butylsilyloxy-3-methylbutoxy]-4-methoxy-5-thiophen-2-ylbenzaldehyde

HRID 10685Notes

Reaction equation

HRID 10685 reaction equation
[OH:1][C:2]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([C:12]2[S:13][CH:14]=[CH:15][CH:16]=2)=[CH:6][C:3]=1[CH:4]=[O:5].C(=O)([O-])[O-].[K+].[K+].[C:23]([Si:27]([CH3:47])([CH3:46])[O:28][CH2:29][CH:30]([C:37]([CH3:45])([CH3:44])[O:38][SiH2:39][C:40]([CH3:43])([CH3:42])[CH3:41])[CH2:31]OS(C)(=O)=O)([CH3:26])([CH3:25])[CH3:24]>CN(C)C=O.O>[C:23]([Si:27]([CH3:46])([CH3:47])[O:28][CH2:29][CH:30]([C:37]([CH3:45])([CH3:44])[O:38][SiH2:39][C:40]([CH3:43])([CH3:42])[CH3:41])[CH2:31][O:1][C:2]1[CH:9]=[C:8]([O:10][CH3:11])[C:7]([C:12]2[S:13][CH:14]=[CH:15][CH:16]=2)=[CH:6][C:3]=1[CH:4]=[O:5])([CH3:25])([CH3:26])[CH3:24]

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 118589982-Hydroxy-4-methoxy-5-thiophen-2-yl-benzaldehydeHCID 131725898Methanesulfonic acid 3-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-propyl ester

Product 1

HCID 1317259012-[2-[[Tert-butyl(dimethyl)silyl]oxymethyl]-3-tert-butylsilyloxy-3-methylbutoxy]-4-methoxy-5-thiophen-2-ylbenzaldehydeYield 81%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
80 °C

Procedure

Ex-64A: To a solution of 2-hydroxy-4-methoxy-5-thiophen-2-yl-benzaldehyde (10.0 g, 42.7 mmol) in N,N-dimethylformamide (100 mL) was added potassium carbonate (11.8 g, 85.4 mmol) and the resulting yellow slurry was heated to 80° C. Once at 80° C., methanesulfonic acid 3-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-propyl ester (Ex-50A, 19.5 g, 46.9 mmol) was added dropwise and the reaction was stirred for an additional 24 h at 80° C. and cooled to room temperature. The mixture was diluted with water (500 mL) and extracted with ethyl acetate (3×150 mL). The combined organic layers was sequentially washed with a saturated sodium bicarbonate solution (1×150 mL), water (1×150 mL), and brine (1×150 mL), dried over sodium sulfate, and concentrated to a brown oil. Silica gel chromatography (100% ethyl acetate to 10% ethyl acetate/hexanes) gave 19.0 g (81%) of 2-[3-(tert-butyl-dimethyl-silanyloxy)-2-(tert-butyl-dimethyl-silanyloxymethyl)-propoxy]-4-methoxy-5-thiophen-2-yl-benzaldehyde as an off-white solid, mp 91–92° C. 1H-NMR (300 MHz, CDCl3) δ 10.37 (s, 1H), 8.12 (s, 1H), 7.44 (dd, 1H, J=3.6, 1.2 Hz), 7.29 (d, 1H, J=5.1 Hz), 7.07 (dd, 1H, J=5.1, 3.6 Hz), 6.54 (s, 1H), 4.19 (d, 2H, J=6.0 Hz), 3.99 (s, 3H), 3.72–3.82 (m, 4H), 2.28 (pentet, 1H, J=6.0 Hz), 0.88 (s, 18H), 0.048 (s, 12H). MS (EI) m/z=550 ([M]+, 100%). Anal. Calcd. for C28H46O5SSi2: C, 61.05; H, 8.42; S, 5.82. Found: C, 61.20; H, 8.74; S, 5.69.

Workup

  1. temperaturecooled to room temperature
  2. extractionextracted with ethyl acetate (3×150 mL)
  3. washThe combined organic layers was sequentially washed with a saturated sodium bicarbonate solution (1×150 mL), water (1×150 mL), and brine (1×150 mL)
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated to a brown oil

Sources & evidence

ORD record
ord-465275cc1e2146188b98a388bd049399
Source dataset
uspto-grants-2006_08
Patent number
US07094801B2

Reaction notes

Loading…