Cesium carbonate → 3-{2-[2-(2-{2-Azidoethoxy}ethoxy)ethoxy]ethoxy}-4,5-dimethoxybenzaldehyde

HRID 1510971Notes

Reaction equation

HRID 1510971 reaction equation
CS([O:5][CH2:6][CH2:7][O:8][CH2:9][CH2:10][O:11][CH2:12][CH2:13][O:14][CH2:15][CH2:16][N:17]=[N+:18]=[N-:19])(=O)=O.[CH3:20][O:21][C:22]1[C:29]([O:30][CH3:31])=[CH:28][C:25]([CH:26]=[O:27])=[CH:24][C:23]=1O.C(=O)([O-])[O-].[Cs+].[Cs+].[Cl-].[NH4+]>CN(C=O)C>[N:17]([CH2:16][CH2:15][O:14][CH2:13][CH2:12][O:11][CH2:10][CH2:9][O:8][CH2:7][CH2:6][O:5][C:23]1[CH:24]=[C:25]([CH:28]=[C:29]([O:30][CH3:31])[C:22]=1[O:21][CH3:20])[CH:26]=[O:27])=[N+:18]=[N-:19]

Participants

6

Reactant 4

HCID 10796Cesium carbonateHCID 25517Ammonium ChlorideHCID 1415133,4-Dimethoxy-5-hydroxybenzaldehydeHCID 148276732-(2-(2-(2-Azidoethoxy)ethoxy)ethoxy)ethyl methanesulfonate

Product 1

HCID 866321223-{2-[2-(2-{2-Azidoethoxy}ethoxy)ethoxy]ethoxy}-4,5-dimethoxybenzaldehydeYield 68.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
50 °C

Procedure

A mixture of 5.22 g (17.55 mmol) 2-{2-[2-(2-azidoethoxy)ethoxy]ethoxy}ethyl methanesulfonate 7, 3.20 g (17.55 mmol) 3,4-dimethoxy-5-hydroxybenzaldehyde 1 and 11.5 g (35.20 mmol) caesium carbonate in 120 ml DMF was heated at 50° C. for 17 hrs. The mixture was poured into 100 ml saturated aqueous ammonium chloride solution and extracted with methylene chloride. The combined organic layers were washed with water and brine, dried over MgSO4 and evaporated. The residue was purified by silica gel column chromatography (toluene/ethyl acetate 1/1), yielding 4.58 g (11.95 mmol, 68%) of the product as a clear yellow oil. 1H-NMR (CDCl3) δ=9.77 (s, 1H), 7.09 (d, 1H, J=2.2 Hz), 7.06 (d, 1H, J=2.2 Hz), 4.17 (m, 2H), 3.88 (s, 3H), 3.85 (s, 3H), 3.83 (m, 2H), 3.66 (m, 2H), 3.60 (m, 8H), 3.30 (t, 2H, J=5.4 Hz) ppm. 13C-NMR δ=190.7, 153.6, 152.7, 144.2, 131.5, 109.0, 106.4, 70.7, 70.6, 70.5 (2 signals), 69.8, 69.5, 68.8, 60.8, 56.1, 50.5 ppm. MS: m/z=383 [M]+. Anal. calcd for C17H25N3O7: C, 53.26, H, 6.57, N, 10.96. Found C, 53.15, H, 6.66, N, 10.99.

Workup

  1. extractionextracted with methylene chloride
  2. washThe combined organic layers were washed with water and brine
  3. dry with materialdried over MgSO4
  4. customevaporated
  5. customThe residue was purified by silica gel column chromatography (toluene/ethyl acetate 1/1)

Sources & evidence

ORD record
ord-a00889877fe14cf7ad1ce7837465eefc
Source dataset
uspto-grants-2012_07
Patent number
US08212058B2

Reaction notes

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