Nitric Acid → Isoidide mononitrate

HRID 1643411Notes

Reaction equation

HRID 1643411 reaction equation
[N+:1]([O-:4])([OH:3])=[O:2].C(OC(=O)C)(=O)C.[CH2:12]1[O:16][C@@H:15]2[C@H:17]([OH:20])[CH2:18][O:19][C@@H:14]2[C@@H:13]1O>C(Cl)Cl>[N+:1]([O-:4])([O:3][C@@H:13]1[CH2:12][O:16][C@@H:15]2[C@H:17]([OH:20])[CH2:18][O:19][C@H:14]12)=[O:2]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 7918Acetic AnhydrideHCID 109756241,4:3,6-Dianhydro-D-mannitol

Product 1

HCID 182267Isoidide mononitrateYield 41.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of fuming nitric acid (0.92 mL, 22.2 mmol) in CH2Cl2 (44 mL) and acetic anhydride (2.10 mL, 22.2 mmol) cooled to −20° C., 1,4:3,6-dianhydro-D-mannitol (2.50 g, 17.1 mmol) was added as solid. After the reaction mixture was stirred at 0° C. for 3 hours, it was slowly poured into ice/NaHCO3. The organic layer was separated, dried over Na2SO4 and concentrated under reduced pressure. The crude residue was purified by flash chromatography (Biotage SP1, column SNAP 100, EtOAc/n-hexane from 30 to 100%), affording the title product as a white solid (1.35 g, yield 41%). 1H-NMR (300 MHz, CDCl3); δ 5.39 (1H, q), 4.89 (1H, t), 4.49 (1H, t), 4.35-4.27 (1H, m), 4.10-4.04 (2H, m), 3.58 (2H, t), 2.40 (1H, d).

Workup

  1. customThe organic layer was separated
  2. dry with materialdried over Na2SO4
  3. concentrationconcentrated under reduced pressure
  4. customThe crude residue was purified by flash chromatography (Biotage SP1, column SNAP 100, EtOAc/n-hexane from 30 to 100%)

Sources & evidence

ORD record
ord-a14b0d637a774461a5b012cefe5a232f
Source dataset
uspto-grants-2012_02
Patent number
US08119806B2

Reaction notes

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