Methyl Gallate → Methyl 3,4,5-tris(2-(2-(2-azidoethoxy)ethoxy)ethoxy)benzoate

HRID 531421Notes

Reaction equation

HRID 531421 reaction equation
CC1C=CC(S(O[CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][N:20]=[N+:21]=[N-:22])(=O)=O)=CC=1.[C:23]([O-:26])([O-])=O.[K+].[K+].[C:29]([O:40][CH3:41])(=[O:39])[C:30]1[CH:38]=[C:36]([OH:37])[C:34]([OH:35])=[C:32]([OH:33])[CH:31]=1>CC(C)=O.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC>[N:20]([CH2:19][CH2:18][O:17][CH2:16][CH2:15][O:14][CH2:13][CH2:12][O:37][C:36]1[CH:38]=[C:30]([CH:31]=[C:32]([O:33][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][N:20]=[N+:21]=[N-:22])[C:34]=1[O:35][CH2:12][CH2:13][O:14][CH2:15][CH2:16][O:26][CH2:23][CH2:19][N:20]=[N+:21]=[N-:22])[C:29]([O:40][CH3:41])=[O:39])=[N+:21]=[N-:22]

Participants

6

Reactant 3

HCID 7428Methyl GallateHCID 11430Potassium CarbonateHCID 577736862-(2-(2-Azidoethoxy)ethoxy)ethyl 4-methylbenzenesulfonate

Product 1

HCID 54589774Methyl 3,4,5-tris(2-(2-(2-azidoethoxy)ethoxy)ethoxy)benzoateYield 94.2%

Reagents, catalysts & solvents 2

HCID 74236Tetrabutylammonium BromideCatalystHCID 180AcetoneSolvent

Procedure

To a solution in which the 2-(2-(2-azidoethoxy)ethoxy)ethyl 4-methylbenzenesulfonate (4.80 g, 14.57 mmol) compound of Chemical Formula 9 was dissolved in acetone (15 mL), K2CO3 (2.05 g, 14.85 mmol), the methyl gallate (650.9 mg, 3.53 mmol) compound of Chemical Formula 10 and tetrabutylammonium bromide (25 mg) were added consecutively at room temperature. The reaction mixture was heated under reflux for 17 hours, cooled to room temperature, and partitioned to distilled water (40 mL) and ethyl acetate (150 mL). The organic layer was separated, washed with saturated salted water (15 mL), dried with anhydrous sodium sulfate, filtered and vacuum distilled, and the residue obtained was column chromatographed on silica gel (hexane/ethyl acetate (1:1.5)) to give methyl 3,4,5-tris(2-(2-(2-azidoethoxy)ethoxy)ethoxy)benzoate (2.18 g, 94%). 1H NMR (500 MHz, CDCl3) δ 7.29 (s, 2H), 4.18-4.23 (m, 6H), 3.86-3.88 (m, 7H), 3.81 (t, 2H, J=5.0 Hz), 3.70-3.74 (m, 6H), 3.63-3.67 (m, 12H), 3.36-3.39 (m, 6H).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux for 17 hours
  3. custompartitioned
  4. distillationto distilled water (40 mL) and ethyl acetate (150 mL)
  5. customThe organic layer was separated
  6. washwashed with saturated salted water (15 mL)
  7. dry with materialdried with anhydrous sodium sulfate
  8. filtrationfiltered
  9. distillationvacuum distilled
  10. customthe residue obtained
  11. customchromatographed on silica gel (hexane/ethyl acetate (1:1.5))

Sources & evidence

ORD record
ord-b794e5aca8464f559db05714577398d8
Source dataset
uspto-grants-2016_05
Patent number
US09354234B2

Reaction notes

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