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 1896131Notes

Reaction equation

HRID 1896131 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, 1 H), 7.79 (d, J=2.78 Hz, 1 H), 7.24 (d, J=9.12 Hz, 1 H), 3.86-4.10 (m, 2 H), 3.36-3.50 (m, 1 H), 3.20-3.29 (m, 1 H), 2.81-2.99 (m, 1 H), 2.62-2.77 (m, 1 H), 2.18 (d, J=13.48 Hz, 1 H); 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-18c6d34bb7464394956ea9fcb988ffc5
Source dataset
uspto-grants-2013_08
Patent number
US08518933B2

Reaction notes

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