1,4-Dioxane → HCID 117716656, compound

HRID 1398265Notes

Reaction equation

HRID 1398265 reaction equation
[NH2:1][C:2]1[CH:31]=[CH:30][C:5]([O:6][CH:7]([CH3:29])[C:8]([O:10][CH2:11][CH2:12][O:13][CH2:14][CH2:15][O:16][C:17](=[O:28])[CH:18]([O:20][C:21]2[CH:26]=[CH:25][C:24]([NH2:27])=[CH:23][CH:22]=2)[CH3:19])=[O:9])=[CH:4][CH:3]=1.Cl[C:33](Cl)([O:35]C(=O)OC(Cl)(Cl)Cl)Cl.[O:44]1CCOC[CH2:45]1>>[N:27]([C:24]1[CH:23]=[CH:22][C:21]([O:20][CH:18]([CH3:19])[C:17]([O:16][CH2:15][CH2:14][O:13][CH2:12][CH2:11][O:10][C:8](=[O:9])[CH:7]([O:6][C:5]2[CH:4]=[CH:3][C:2]([N:1]=[C:45]=[O:44])=[CH:31][CH:30]=2)[CH3:29])=[O:28])=[CH:26][CH:25]=1)=[C:33]=[O:35]

Participants

4

Reactant 3

HCID 312751,4-Dioxane2×HCID 94429TriphosgeneHCID 117716311HCID 117716311, compound

Product 1

HCID 117716656HCID 117716656, compound

Conditions

Temperature
80 °C

Procedure

(4-Aminophenoxy)-propionic acid 2-{2-[2-(4-aminophenoxy)-propionyloxy]-ethoxy}-ethyl ester (217 g) was dissolved in dry 1,4-dioxane (2 L) under nitrogen atmosphere. The reaction mixture was cooled down to below 10° C. A solution of triphosgene (253 g) in dry 1,4-dioxane (600 ml) was added. The mixture was heated slowly to 80° C. and maintained at that temperature for 2 hours. The condenser was then arranged for distillation and solvent removed by distillation under atmospheric pressure until the volume of the reaction mixture had been reduced to approximately one third. Fresh dry 1,4-dioxane (600 ml) was added. Solvents were distilled off under vacuum. The residue was re-evaporated two times from dry 1,4-dioxane (1200 ml). Dry toluene (600 ml) and charcoal (50 g) was added. The solution was filtered hot and toluene was distilled off under vacuum to give pure (4-isocyanato-phenoxy)-propionic acid 2-{2-[2-(4-isocyanato-phenoxy)-propionyloxy]-ethoxy}-ethyl ester (165 g) as a light yellow syrup. The product was characterized by 1H NMR (CDCl3) δ 1.65 (d, 3H, CH3), 3.65 (t, 2H, CH2), 4.30 (t, 2H, CH2), 4.75 (q, 1H, CH), 6.80 (d, 2H, Ar), 7.00 (d, 2H, Ar).

Workup

  1. temperatureThe reaction mixture was cooled down to below 10° C
  2. temperaturemaintained at that temperature for 2 hours
  3. distillationThe condenser was then arranged for distillation and solvent
  4. customremoved by distillation under atmospheric pressure until the volume of the reaction mixture
  5. additionFresh dry 1,4-dioxane (600 ml) was added
  6. distillationSolvents were distilled off under vacuum
  7. customThe residue was re-evaporated two times from dry 1,4-dioxane (1200 ml)
  8. additionDry toluene (600 ml) and charcoal (50 g) was added
  9. filtrationThe solution was filtered hot
  10. distillationtoluene was distilled off under vacuum

Sources & evidence

ORD record
ord-3552c91fde0c4b2aa72314992667dffa
Source dataset
uspto-grants-2014_12
Patent number
US08901347B1

Reaction notes

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