1,4-Dioxane → Ethane-1,2-diyl bis(2-(4-isocyanatophenoxy)acetate)

HRID 1957850Notes

Reaction equation

HRID 1957850 reaction equation
[NH2:1][C:2]1[CH:26]=[CH:25][C:5]([O:6][CH2:7][C:8]([O:10][CH2:11][CH2:12][O:13][C:14](=[O:24])[CH2:15][O:16][C:17]2[CH:22]=[CH:21][C:20]([NH2:23])=[CH:19][CH:18]=2)=[O:9])=[CH:4][CH:3]=1.Cl[C:28](Cl)([O:30]C(=O)OC(Cl)(Cl)Cl)Cl.[O:39]1CCOC[CH2:40]1>>[N:23]([C:20]1[CH:19]=[CH:18][C:17]([O:16][CH2:15][C:14]([O:13][CH2:12][CH2:11][O:10][C:8](=[O:9])[CH2:7][O:6][C:5]2[CH:25]=[CH:26][C:2]([N:1]=[C:40]=[O:39])=[CH:3][CH:4]=2)=[O:24])=[CH:22][CH:21]=1)=[C:28]=[O:30]

Participants

4

Reactant 3

HCID 312751,4-Dioxane2×HCID 94429TriphosgeneHCID 25235089(4-Amino-phenoxy)-acetic acid-2-[2-(4-amino-phenoxy)-acetoxy]-ethyl ester

Product 1

HCID 49764366Ethane-1,2-diyl bis(2-(4-isocyanatophenoxy)acetate)Yield 44.2%

Conditions

Temperature
77.5 °C

Procedure

(4-Aminophenoxy)acetic acid 2-[2-(4-aminophenoxy)acetoxy]ethyl ester 43 (5 g, 14.3 mmol) was dissolved in dry dioxane (80 ml) under nitrogen atm. and cooled to below 20° C. A solution of triphosgene (7 g, 23.6 mmol) in dry dioxane (20 ml) was added drop wise. The mixture was heated slowly to 75-80° C. and maintained for 2½ 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 (50 ml) was added and the solvents were distilled off under vacuum. The residue was re-evaporated two times from dry dioxane to give crude 44. Crude 44 was recrystallised from a mixture of toluene:hexane (1:3) to give pure 44 (2.6 g, 44.2%) as a white powder. M.p: 96-98° C.

Workup

  1. temperatureand cooled to below 20° C
  2. temperaturemaintained for 2½ hours
  3. distillationThe condenser was then arranged for distillation and solvent
  4. customremoved by distillation at atmospheric pressure until the volume of the reaction mixture
  5. additionFresh dry dioxane (50 ml) was added
  6. distillationthe solvents were distilled off under vacuum
  7. customThe residue was re-evaporated two times from dry dioxane
  8. customto give crude 44
  9. customCrude 44 was recrystallised from a mixture of toluene:hexane (1:3)

Sources & evidence

ORD record
ord-254490fe553a49ff88efab97c1c23595
Source dataset
uspto-grants-2013_04
Patent number
US08409559B2

Reaction notes

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