Nitric Acid → Tert-butyl 9-nitro-6-oxo-1,2,4a,5,6,7-hexahydropyrazino[1,2-a][1,5]benzodiazepine-3(4h)-carboxylate

HRID 1035294Notes

Reaction equation

HRID 1035294 reaction equation
[N+:1]([O-:4])(O)=[O:2].[O:5]=[C:6]1[NH:12][C:11]2[CH:13]=[CH:14][CH:15]=[CH:16][C:10]=2[N:9]2[CH2:17][CH2:18][N:19]([C:21]([O:23][C:24]([CH3:27])([CH3:26])[CH3:25])=[O:22])[CH2:20][CH:8]2[CH2:7]1.O>C(O)(=O)C>[N+:1]([C:14]1[CH:15]=[CH:16][C:10]2[N:9]3[CH2:17][CH2:18][N:19]([C:21]([O:23][C:24]([CH3:25])([CH3:26])[CH3:27])=[O:22])[CH2:20][CH:8]3[CH2:7][C:6](=[O:5])[NH:12][C:11]=2[CH:13]=1)([O-:4])=[O:2]

Participants

5

Reactant 3

HCID 944Nitric AcidHCID 962WaterHCID 58284919tert-butyl 6-oxo-1,2,4a,5,6,7-hexahydropyrazino[1,2-a][1,5]benzodiazepine-3(4H)-carboxylate

Product 1

HCID 67249636Tert-butyl 9-nitro-6-oxo-1,2,4a,5,6,7-hexahydropyrazino[1,2-a][1,5]benzodiazepine-3(4h)-carboxylate

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Nitric acid (65% solution, 0.20 mL, 3.2 mmol) was added to a solution of Example 1C (1.0 g, 3.2 mmol) in acetic acid (5 mL) at room temperature. The solution was stirred for 3 hours, and then the reaction mixture was poured into water (200 mL). The precipitate was collected by filtration from the aqueous solution to afford the title compound. 1H NMR (300 MHz, DMSO-d6) d ppm 8.00 (dd, J=8.92, 2.58 Hz, 1H), 7.79 (d, J=2.78 Hz, 1H), 7.24 (d, J=9.12 Hz, 1H), 3.86-4.10 (m, 2H), 3.36-3.50 (m, 1H), 3.20-3.29 (m, 1H), 2.81-2.99 (m, 1H), 2.62-2.77 (m, 1H), 2.18 (d, J=13.48 Hz, 1H); MS (APCI+) m/z 307 (M+H-tBu)+.

Workup

  1. filtrationThe precipitate was collected by filtration from the aqueous solution

Sources & evidence

ORD record
ord-d235f719dcca4728be3031d87cdf2447
Source dataset
uspto-grants-2013_10
Patent number
US08546377B2

Reaction notes

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