2-[2,4-Dioxo-3-(phenyl-hydrazono)-5-(1,3,5-trimethyl-1H-pyrazol-4-yl)-2,3,4,5-tetrahydro-benzo[b][1,4]diazepin-1-yl]-N-isopropyl-N-(4-methoxy-phenyl)-acetamide → 2-[3-Amino-2,4-dioxo-5-(1,3,5-trimethyl-1H-pyrazol-4-yl)-2,3,4,5-tetrahydro-benzo[b][1,4]diazepin-1-yl]-N-isopropyl-N-(4-methoxy-phenyl)-acetamide

HRID 1599085Notes

Reaction equation

HRID 1599085 reaction equation
[O:1]=[C:2]1[N:8]([CH2:9][C:10]([N:12]([CH:21]([CH3:23])[CH3:22])[C:13]2[CH:18]=[CH:17][C:16]([O:19][CH3:20])=[CH:15][CH:14]=2)=[O:11])[C:7]2[CH:24]=[CH:25][CH:26]=[CH:27][C:6]=2[N:5]([C:28]2[C:29]([CH3:35])=[N:30][N:31]([CH3:34])[C:32]=2[CH3:33])[C:4](=[O:36])[C:3]1=[N:37]NC1C=CC=CC=1>C(O)(=O)C.[Zn]>[NH2:37][CH:3]1[C:2](=[O:1])[N:8]([CH2:9][C:10]([N:12]([CH:21]([CH3:23])[CH3:22])[C:13]2[CH:14]=[CH:15][C:16]([O:19][CH3:20])=[CH:17][CH:18]=2)=[O:11])[C:7]2[CH:24]=[CH:25][CH:26]=[CH:27][C:6]=2[N:5]([C:28]2[C:29]([CH3:35])=[N:30][N:31]([CH3:34])[C:32]=2[CH3:33])[C:4]1=[O:36]

Participants

4

Reactant 1

HCID 543449192-[2,4-Dioxo-3-(phenyl-hydrazono)-5-(1,3,5-trimethyl-1H-pyrazol-4-yl)-2,3,4,5-tetrahydro-benzo[b][1,4]diazepin-1-yl]-N-isopropyl-N-(4-methoxy-phenyl)-acetamide

Product 1

HCID 189295692-[3-Amino-2,4-dioxo-5-(1,3,5-trimethyl-1H-pyrazol-4-yl)-2,3,4,5-tetrahydro-benzo[b][1,4]diazepin-1-yl]-N-isopropyl-N-(4-methoxy-phenyl)-acetamideYield 9.9%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 176Acetic AcidSolvent

Procedure

To a solution of 2-[2,4-Dioxo-3-(phenyl-hydrazono)-5-(1,3,5-trimethyl-1H-pyrazol-4-yl)-2,3,4,5-tetrahydro-benzo[b][1,4]diazepin-1-yl]-N-isopropyl-N-(4-methoxy-phenyl)-acetamide (4.6 g, 7.74 mmol) in glacial acetic acid (45 mL) was added zinc dust (4.6 g). The heterogenous solution stirred at RT for 15 h and subsequently filtered through a bed of celite, washed with ethyl acetate and concentrated to dryness. The resulting oil was dissolved in ethyl acetate (200 mL) and extracted with saturated sodium bicarbonate (×3), brine, dried MgSO4, and concentrated in vacuo. The resulting oil was purified by silica gel flash chromatography (5% methanol/DCM) to yield the title compound (385 mg): 1HNMR (CDCl3, 300 MHz) δ 7.60-6.80 (m, 10H), 5.05 (m, 1H), 4.4(m, 1H), 3.82 (s, 3H), 3.74 (s, 3H), 3.62 (s, 2H), 2.24 (s, 3H), 1.20 (s, 3H), 1.09 (m, 6H); low resolution MS(FAB) m/z 505 (MH+).

Workup

  1. filtrationsubsequently filtered through a bed of celite
  2. washwashed with ethyl acetate
  3. concentrationconcentrated to dryness
  4. dissolutionThe resulting oil was dissolved in ethyl acetate (200 mL)
  5. extractionextracted with saturated sodium bicarbonate (×3), brine, dried MgSO4
  6. concentrationconcentrated in vacuo
  7. customThe resulting oil was purified by silica gel flash chromatography (5% methanol/DCM)

Sources & evidence

ORD record
ord-64249aefd34e42b29f36c7098720424e
Source dataset
uspto-grants-1998_04
Patent number
US05739129

Reaction notes

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