1,4-Dioxane → HCID 90308342, compound

HRID 1398261Notes

Reaction equation

HRID 1398261 reaction equation
[NH2:1][C:2]1[CH:29]=[CH:28][C:5]([O:6][CH2:7][C:8]([O:10][CH2:11][CH2:12][O:13][CH2:14][CH2:15][O:16][C:17](=[O:27])[CH2:18][O:19][C:20]2[CH:25]=[CH:24][C:23]([NH2:26])=[CH:22][CH:21]=2)=[O:9])=[CH:4][CH:3]=1.Cl[C:31](Cl)([O:33]C(=O)OC(Cl)(Cl)Cl)Cl.[O:42]1CCOC[CH2:43]1>>[N:26]([C:23]1[CH:22]=[CH:21][C:20]([O:19][CH2:18][C:17]([O:16][CH2:15][CH2:14][O:13][CH2:12][CH2:11][O:10][C:8](=[O:9])[CH2:7][O:6][C:5]2[CH:4]=[CH:3][C:2]([N:1]=[C:43]=[O:42])=[CH:29][CH:28]=2)=[O:27])=[CH:25][CH:24]=1)=[C:31]=[O:33]

Participants

4

Reactant 3

HCID 312751,4-Dioxane2×HCID 94429TriphosgeneHCID 117716287HCID 117716287, compound

Product 1

HCID 90308342HCID 90308342, compound

Conditions

Temperature
80 °C

Procedure

(4-Aminophenoxy)-acetic acid 2-{2-[2-(4-aminophenoxy)-acetoxy]-ethoxy}-ethyl ester (200 grams, 495 mmoles) was dissolved in dry 1,4-dioxane (2000 ml) under nitrogen atmosphere and cooled to below 10° C. A solution of triphosgene (250 grams, 842.45 mmoles) 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 the solvent was removed by distillation at 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 and distilled off under vacuum. The residue was re-evaporated two times from dry 1,4-dioxane (1.2 L), then dry toluene (600 ml) and charcoal (20 g) were added. The solution was filtered hot, and toluene was distilled off under vacuum to give pure (4-isocyanato-phenoxy)-acetic acid 2-{2-[2-(4-isocyanato-phenoxy)-acetoxy]-ethoxy}-ethyl ester (4.5 g) as a light yellow syrup. The product was characterized by 1H NMR (CDCl3) δ 3.65 (t, 2H, CH2), 4.35 (t, 2H, CH2), 4.65 (s, 2H, CH2), 6.75 (d, 2H, Ar), 7.00 (d, 2H, Ar).

Workup

  1. temperaturecooled to below 10° C
  2. temperaturemaintained at that temperature for 2 hours
  3. distillationThe condenser was then arranged for distillation
  4. customthe solvent was removed by distillation at atmospheric pressure until the volume of the reaction mixture
  5. additionFresh dry 1,4-dioxane (600 ml) was added
  6. distillationdistilled off under vacuum
  7. customThe residue was re-evaporated two times from dry 1,4-dioxane (1.2 L)
  8. additiondry toluene (600 ml) and charcoal (20 g) were added
  9. filtrationThe solution was filtered hot
  10. distillationtoluene was distilled off under vacuum

Sources & evidence

ORD record
ord-aba5ba0534b24244a3dae55b7f1b73b7
Source dataset
uspto-grants-2014_12
Patent number
US08901347B1

Reaction notes

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