Nitric Acid → Methyl 7-Nitro-1,4-benzodioxane-6-carboxylate

HRID 1908957Notes

Reaction equation

HRID 1908957 reaction equation
[O:1]1[CH2:6][CH2:5][O:4][C:3]2[CH:7]=[C:8]([C:11]([O:13][CH3:14])=[O:12])[CH:9]=[CH:10][C:2]1=2.[N+:15]([O-])([OH:17])=[O:16]>C(O)(=O)C>[N+:15]([C:9]1[C:8]([C:11]([O:13][CH3:14])=[O:12])=[CH:7][C:3]2[O:4][CH2:5][CH2:6][O:1][C:2]=2[CH:10]=1)([O-:17])=[O:16]

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 3802178Methyl 2,3-dihydro-1,4-benzodioxine-6-carboxylate

Product 1

HCID 10537941Methyl 7-Nitro-1,4-benzodioxane-6-carboxylateYield 92%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution of methyl 2,3-dihydrobenzo[b][1,4]dioxine-6-carboxylate (780 mg, 4.0 mmol) in acetic acid (3 mL) was added dropwise conc. HNO3 (4 mL) while keeping the temperature below 20° C. and the resulting reaction mixture was warmed to room temperature. After stirring for 1 hr, the mixture was poured onto ice-water with vigorous stirring. The resulting white precipitate was collected by vacuum filtration and dried under reduced pressure to yield methyl 7-nitro-2,3-dihydrobenzo[b][1,4]dioxine-6-carboxylate (889 mg, 92%). 1H NMR (DMSO-d6, 600 MHz) δ 7.64 (s, 1H), 7.30 (s, 1H), 4.41-4.38 (m, 4H), 3.80 (s, 3H); MS (ES+) m/z 240.0 (M+H)+

Workup

  1. customthe temperature below 20° C.
  2. customthe resulting reaction mixture
  3. additionthe mixture was poured onto ice-water with vigorous stirring
  4. filtrationThe resulting white precipitate was collected by vacuum filtration
  5. customdried under reduced pressure

Sources & evidence

ORD record
ord-e2fdc821153a4475a1f2db61966af86b
Source dataset
uspto-grants-2013_12
Patent number
US08598342B2

Reaction notes

Loading…