2-Methyltetrahydrofuran → 1-Amino-4-(tert-butoxycarbonylamino)pyridinium 2,4-dinitrophenolate

HRID 513032

Reaction equation

HRID 513032 reaction equation
[N+:1]([C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[O:13]N)([O-:3])=[O:2].CC1OCCC1.[N:21]1[CH:26]=[CH:25][C:24]([NH:27][C:28](=[O:34])[O:29][C:30]([CH3:33])([CH3:32])[CH3:31])=[CH:23][CH:22]=1>>[N+:1]([C:4]1[CH:9]=[C:8]([N+:10]([O-:12])=[O:11])[CH:7]=[CH:6][C:5]=1[O-:13])([O-:3])=[O:2].[NH2:1][N+:21]1[CH:22]=[CH:23][C:24]([NH:27][C:28]([O:29][C:30]([CH3:31])([CH3:33])[CH3:32])=[O:34])=[CH:25][CH:26]=1

Participants

4

Reactant 3

HCID 73012-Methyltetrahydrofuran2×HCID 87140O-(2,4-dinitrophenyl)hydroxylamineHCID 99902104-(Boc-amino)pyridine

Product 1

HCID 867050031-Amino-4-(tert-butoxycarbonylamino)pyridinium 2,4-dinitrophenolate

Procedure

To a 3 L four-necked flask equipped with an overhead stirrer, thermocouple and a condenser was charged with O-(2,4-dinitrophenyl)hydroxylamine (I-37) (248 g, 1245.5 mmol) and 2-MeTHF (1 L). To the stirred suspension at room temperature were added tert-butyl pyridin-4-ylcarbamate (254.6 g, 1245.5 mmol) and 2-MeTHF (1 L). The mixture was stirred at room temperature for 10 minutes and slowly heated to 40° C. (after 30 minutes the suspension became a solution at 30° C.). An exotherm was observed at 40° C. and the temperature reached 45° C. without heating. The mixture was cooled with a water bath to 40° C. and stirred at 40° C. for 4 hours. The mixture was further cooled to room temperature and stirred for 15 hours. The batch was filtered and the solid was washed with MTBE (2×200 mL) and air dried to give 1-amino-4-(tert-butoxycarbonylamino)pyridinium 2,4-dinitrophenolate (I-38) as a yellow solid. 1H NMR (500 MHz, DMSO) δ 10.90 (s, 1 H), 8.62 (s, 1 H), 8.54 (d, 2 H), 7.91 (d, 2 H), 7.85 (m, 3 H), 6.30 (d, 1 H), 1.46 (s, 9 H).

Workup

  1. customTo a 3 L four-necked flask equipped with an overhead stirrer
  2. temperatureslowly heated to 40° C. (after 30 minutes the suspension
  3. customat 30° C.
  4. customwas observed at 40° C.
  5. customreached 45° C.
  6. temperaturewithout heating
  7. temperatureThe mixture was cooled with a water bath to 40° C.
  8. stirringstirred at 40° C. for 4 hours
  9. temperatureThe mixture was further cooled to room temperature
  10. stirringstirred for 15 hours
  11. filtrationThe batch was filtered
  12. washthe solid was washed with MTBE (2×200 mL) and air
  13. customdried

Sources & evidence

ORD record
ord-78ef8da725164011a63adffceae06615
Source dataset
uspto-grants-2015_08
Patent number
US09102671B2

Linked notes

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