Diphosgene → HCID 57626829, compound

HRID 554063Notes

Reaction equation

HRID 554063 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([O:8][C:9](=[O:23])[CH2:10][O:11][CH2:12][C:13]([O:15][C:16]2[CH:21]=[CH:20][C:19]([NH2:22])=[CH:18][CH:17]=2)=[O:14])=[CH:4][CH:3]=1.[O:24]=[C:25](Cl)OC(Cl)(Cl)Cl.[O:32]1CCOC[CH2:33]1>>[N:22]([C:19]1[CH:18]=[CH:17][C:16]([O:15][C:13](=[O:14])[CH2:12][O:11][CH2:10][C:9]([O:8][C:5]2[CH:6]=[CH:7][C:2]([N:1]=[C:33]=[O:32])=[CH:3][CH:4]=2)=[O:23])=[CH:21][CH:20]=1)=[C:25]=[O:24]

Participants

4

Reactant 3

HCID 10426DiphosgeneHCID 312751,4-Dioxane2×HCID 25234030HCID 25234030, compound

Product 1

HCID 57626829HCID 57626829, compound

Conditions

Temperature
100 °C

Procedure

To a solution of (4-amino-phenoxycarbonylmethoxy)-acetic acid 4-amino-phenyl ester (27) (2 grams, 6.32 mmoles) in dry 1,4-dioxane (32 ml) under nitrogen atmosphere was cooled to 10° C. and added a solution of diphosgene (4 grams, 13.47 mmoles) in 1,4-dioxane (8 ml) in one lot and heated to a temperature of 100° C. for 2 hours. The condenser was then arranged for distillation and solvent removed by distillation at atmospheric pressure until the volume of the reaction mixture was reduced to approximately one third. Fresh dry dioxane (10 ml) was added and distilled off the solvents under vacuum. The residue was re-evaporated two times from dry dioxane (2×10 ml) to give crude 28 (4-Isocyanato-phenoxycarbonylmethoxy)-acetic acid 4-isocyanato-phenyl ester, which was recrystallized from toluene as a white powder with a melting point of 150.5-152.4° C., IR: 2316.1 cm−1, 2274.3 cm−1. The pure product 28 was also characterized using 1H NMR spectroscopy in CDCl3: δ 4.56 (s, 2H, CH2), 7.10 (s, 4H, Ar).

Workup

  1. distillationThe condenser was then arranged for distillation and solvent
  2. customremoved by distillation at atmospheric pressure until the volume of the reaction mixture
  3. additionFresh dry dioxane (10 ml) was added
  4. distillationdistilled off the solvents under vacuum
  5. customThe residue was re-evaporated two times from dry dioxane (2×10 ml)

Sources & evidence

ORD record
ord-2d72f62af4af487ab2636297f124c30e
Source dataset
uspto-grants-2011_11
Patent number
US08048980B2

Reaction notes

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