1,4-Dioxane → HCID 117716233, compound

HRID 1398269Notes

Reaction equation

HRID 1398269 reaction equation
[NH2:1][C:2]1[CH:37]=[CH:36][C:5]([O:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][C:12]([O:14][CH2:15][CH2:16][O:17][CH2:18][CH2:19][O:20][C:21](=[O:35])[CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][O:27][C:28]2[CH:33]=[CH:32][C:31]([NH2:34])=[CH:30][CH:29]=2)=[O:13])=[CH:4][CH:3]=1.Cl[C:39](Cl)([O:41]C(=O)OC(Cl)(Cl)Cl)Cl.[O:50]1CCOC[CH2:51]1>>[N:34]([C:31]1[CH:30]=[CH:29][C:28]([O:27][CH2:26][CH2:25][CH2:24][CH2:23][CH2:22][C:21]([O:20][CH2:19][CH2:18][O:17][CH2:16][CH2:15][O:14][C:12](=[O:13])[CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][O:6][C:5]2[CH:4]=[CH:3][C:2]([N:1]=[C:51]=[O:50])=[CH:37][CH:36]=2)=[O:35])=[CH:33][CH:32]=1)=[C:39]=[O:41]

Participants

4

Reactant 3

HCID 312751,4-Dioxane2×HCID 94429TriphosgeneHCID 117716327HCID 117716327, compound

Product 1

HCID 117716233HCID 117716233, compound

Conditions

Temperature
80 °C

Procedure

6-(4-Aminophenoxy)-hexanoic acid 2-{2-[6-(4-aminophenoxy)-hexanoyloxy]-ethoxy}-ethyl ester (5 g) was dissolved in dry 1,4-dioxane (80 ml) under nitrogen atmosphere. The solution was cooled to below 10° C. A solution of triphosgene (4.8 g) in dry 1,4-dioxane (20 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 (25 ml) was added. The solvents were distilled off under vacuum. The residue was re-evaporated from dry 1,4-dioxane (50 ml) and dry toluene (30 ml) and charcoal (2 gram) was added. The solution was filtered hot. The toluene was distilled off under vacuum to give pure 6-(4-isocyanatophenoxy)-hexanoic acid 2-{2-[6-(4-isocyanatophenoxy)-hexanoyloxy]-ethoxy}-ethyl ester (4.5 g) as a light yellow oil. The product was characterized by 1H NMR (CDCl3) δ 1.48 (m, 2H, CH2), 1.68 (m, 2H, CH2), 1.78 (m, 2H, CH2), 2.37 (t, 2H, CH2), 3.68 (t, 2H, CH2), 3.92 (t, 2H, CH2), 4.24 (t, 2H, CH2), 6.78 (d, 2H, Ar), 6.97 (d, 2H, Ar).

Workup

  1. temperatureThe solution was cooled 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 (25 ml) was added
  6. distillationThe solvents were distilled off under vacuum
  7. customThe residue was re-evaporated from dry 1,4-dioxane (50 ml) and dry toluene (30 ml) and charcoal (2 gram)
  8. additionwas added
  9. filtrationThe solution was filtered hot
  10. distillationThe toluene was distilled off under vacuum

Sources & evidence

ORD record
ord-c2ef5924b57f4089bcc7bf4f8a9e8ffb
Source dataset
uspto-grants-2014_12
Patent number
US08901347B1

Reaction notes

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