Methyl 7-nitro-2,3-dihydro-1,4-benzodioxine-5-carboxylate → Methyl 7-amino-2,3-dihydro-1,4-benzodioxine-5-carboxylate

HRID 253294Notes

Reaction equation

HRID 253294 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C:14]([O:16][CH3:17])=[O:15])[C:7]2[O:12][CH2:11][CH2:10][O:9][C:8]=2[CH:13]=1)([O-])=O>[Pd].C(OCC)(=O)C>[NH2:1][C:4]1[CH:5]=[C:6]([C:14]([O:16][CH3:17])=[O:15])[C:7]2[O:12][CH2:11][CH2:10][O:9][C:8]=2[CH:13]=1

Participants

4

Reactant 1

HCID 57986654Methyl 7-nitro-2,3-dihydro-1,4-benzodioxine-5-carboxylate

Product 1

HCID 57986620Methyl 7-amino-2,3-dihydro-1,4-benzodioxine-5-carboxylateYield 100%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 8857Ethyl AcetateSolvent

Procedure

Methyl 7-nitro-2,3-dihydro-1,4-benzodioxine-5-carboxylate (5.6 g, 23.4 mmol) and palladium on carbon (250 mg, 30 wt. %) were suspended in ethyl acetate (200 mL). The reaction vessel was evacuated and then immediately filled with hydrogen gas. This deoxygenation process was repeated three times at atmospheric pressure. The black suspension was stirred under a hydrogen atmosphere for 18 h, at which time it was filtered through a bed of Celite and rinsed with ethyl acetate. The filtrate was concentrated, and the residue was triturated with diethyl ether to give 4.89 g (100%) of methyl 7-amino-2,3-dihydro-1,4-benzodioxine-5-carboxylate as an off-white powder: 1H NMR (400 MHz, CDCl3): 6.74 (d, J=2.8 Hz, 1H), 6.40 (d, J=2.8 Hz, 1H), 4.26-4.25 (m, 4H), 3.86 (s, 3H).

Workup

  1. customThe reaction vessel was evacuated
  2. additionimmediately filled with hydrogen gas
  3. filtrationwas filtered through a bed of Celite
  4. washrinsed with ethyl acetate
  5. concentrationThe filtrate was concentrated
  6. customthe residue was triturated with diethyl ether

Sources & evidence

ORD record
ord-9914c2ce47e444d2861abb2f37f84027
Source dataset
uspto-grants-2011_01
Patent number
US07872014B2

Reaction notes

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