Nitric Acid → 7-Nitro-2,3,4,5-tetrahydro-1H-benzo[D]azepine

HRID 1040595Notes

Reaction equation

HRID 1040595 reaction equation
[CH2:1]1[C:7]2[CH:8]=[CH:9][CH:10]=[CH:11][C:6]=2[CH2:5][CH2:4][NH:3][CH2:2]1.[N+:12]([O-])([OH:14])=[O:13]>>[N+:12]([C:9]1[CH:10]=[CH:11][C:6]2[CH2:5][CH2:4][NH:3][CH2:2][CH2:1][C:7]=2[CH:8]=1)([O-:14])=[O:13]

Participants

3

Reactant 2

HCID 944Nitric AcidHCID 14002432,3,4,5-Tetrahydro-1H-benzo(d)azepine

Product 1

HCID 113100427-Nitro-2,3,4,5-tetrahydro-1H-benzo[D]azepine

Procedure

2,3,4,5-Tetrahydro-1H-benzo[d]azepine (535 mg/3.63 mmol, neat) was cooled to −10° C. (acetone/ice bath), treated with neat fuming nitric acid (ca. 10 mL, precooled to −10° C.), and allowed to stir for 30 minutes. The yellow solution was then poured onto ice with vigorous stirring. The resulting white solid was collected by filtration and washed with ice cold water and dried in vacuo to afford the nitrate salt of 7-Nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine as a white solid (650 mg/70%). The filtrate was basified with 1 N sodium hydroxide and extracted with methylene chloride (2×20 mL). The extracts were dried and concentrated to yield an additional 200 mg (25%) of the free base 7-Nitro-2,3,4,5-tetrahydro-1H-benzo[d]azepine. 1H NMR (400 MHz, DMSO-d6) δ 8.87 (br s, 2 H), 8.13 (s, 1H), 8.08 (dd, J=8.1 Hz, 1H), 7.51 (d, J=8.1 Hz, 1H), 3.21 (m, 8H).

Workup

  1. additionThe yellow solution was then poured onto ice with vigorous stirring
  2. filtrationThe resulting white solid was collected by filtration
  3. washwashed with ice cold water
  4. customdried in vacuo

Sources & evidence

ORD record
ord-c65d7526c67940ad9abc96b4588caed8
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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