Ethylene Glycol → 2-(3-{2-[2-(2-{2-Azidoethoxy}ethoxy)ethoxy]ethoxy}-4,5-dimethoxyphenyl)-1,3-dioxolane

HRID 1510973Notes

Reaction equation

HRID 1510973 reaction equation
[N:1]([CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][O:15][C:16]1[CH:17]=[C:18]([CH:21]=[C:22]([O:26][CH3:27])[C:23]=1[O:24][CH3:25])[CH:19]=[O:20])=[N+:2]=[N-:3].[CH2:28](O)[CH2:29][OH:30].C(=O)(O)[O-].[Na+]>C1(C)C=CC=CC=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1>[N:1]([CH2:4][CH2:5][O:6][CH2:7][CH2:8][O:9][CH2:10][CH2:11][O:12][CH2:13][CH2:14][O:15][C:16]1[CH:17]=[C:18]([CH:19]2[O:30][CH2:29][CH2:28][O:20]2)[CH:21]=[C:22]([O:26][CH3:27])[C:23]=1[O:24][CH3:25])=[N+:2]=[N-:3]

Participants

6

Reactant 3

HCID 174Ethylene GlycolHCID 516892Sodium BicarbonateHCID 866321223-{2-[2-(2-{2-Azidoethoxy}ethoxy)ethoxy]ethoxy}-4,5-dimethoxybenzaldehyde

Product 1

HCID 866321212-(3-{2-[2-(2-{2-Azidoethoxy}ethoxy)ethoxy]ethoxy}-4,5-dimethoxyphenyl)-1,3-dioxolaneYield 83.7%

Reagents, catalysts & solvents 2

HCID 521998p-Toluenesulfonic acid monohydrateCatalystHCID 1140TolueneSolvent

Procedure

A mixture of 4.95 g (12.91 mmol) 3-{2-[2-(2-{2-azidoethoxy}ethoxy)ethoxy]ethoxy}-4,5-dimethoxybenzaidehyde 8, 5 ml (5.57 g, 90 mmol) ethylene glycol and 200 mg (1.0 mmol) p-toluene sulfonic acid monohydrate was refluxed in 120 ml of toluene for 8 hrs using a Dean-Stark trap. After cooling to room temperature the rection mixture was poured into 200 ml of diluted sodium bicarbonate solution, washed with water and brine and dried over magnesium sulfate. After removal of the solvent the residue was purified by silica gel column chromatography (cyclohexane/ethyl acetate 1/1), giving 4.43 g (10.8 mmol, 80%) of the product as a clear oil. 1H-NMR (CDCl3) δ=6.73 (dd, 2H, J=5.0 Hz, J=1.8 Hz), 5.72 (s, 1H), 4.19 (m, 2H), 4.11 (m, 2H), 4.03 (m, 2H), 3.87 (s, 3H), 3.84 (s, 3H), 3.76-3.71 (m, 4H), 3.70-3.64 (m, 8H), 3.37 (m, 2H) ppm. 13C-NMR δ=153.3, 152.4, 139.2, 133.1, 105.4, 103.6, 103.4, 70.7, 70.6, 70.5 (2 peaks), 69.9, 69.6, 68.7, 65.1, 60.6, 56.0, 50.6 ppm. MS: m/z=427 [M]+. Anal. calcd for C19H29N3O8: C, 53.39, H, 6.84, N, 9.83. Found C, 52.30, H, 6.89, N, 9.72.

Workup

  1. washwashed with water and brine
  2. dry with materialdried over magnesium sulfate
  3. customAfter removal of the solvent the residue
  4. customwas purified by silica gel column chromatography (cyclohexane/ethyl acetate 1/1)

Sources & evidence

ORD record
ord-fe28c53da1ca4ecca6145d7e78291f8e
Source dataset
uspto-grants-2012_07
Patent number
US08212058B2

Reaction notes

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