Ethyl Acetate → HCID 136229575, compound

HRID 44233Notes

Reaction equation

HRID 44233 reaction equation
Cl[C:2]1[C:3]2[CH:16]=[CH:15][CH:14]=[CH:13][C:4]=2[NH:5][C:6]2[N:12]=[CH:11][CH:10]=[CH:9][C:7]=2[N:8]=1.C(N(C(C)C)CC)(C)C.[NH:26]([C:28]([C:30]1[CH:45]=[CH:44][C:33]([CH2:34][CH2:35][NH:36][C:37](=[O:43])[O:38][C:39]([CH3:42])([CH3:41])[CH3:40])=[CH:32][CH:31]=1)=O)[NH2:27].C(OCC)(=O)C>CN(C)C(=O)C>[N:27]1[N:26]=[C:28]([C:30]2[CH:45]=[CH:44][C:33]([CH2:34][CH2:35][NH:36][C:37](=[O:43])[O:38][C:39]([CH3:40])([CH3:41])[CH3:42])=[CH:32][CH:31]=2)[N:8]2[C:2]=1[C:3]1[CH:16]=[CH:15][CH:14]=[CH:13][C:4]=1[NH:5][C:6]1[N:12]=[CH:11][CH:10]=[CH:9][C:7]2=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 81531DiisopropylethylamineHCID 67434557Tert-butyl 4-(hydrazinecarbonyl)phenethylcarbamateHCID 1361637716-chloro-11H-benzo[e]pyrido[3,2-b][1,4]diazepine

Product 1

HCID 136229575HCID 136229575, compound

Reagents, catalysts & solvents 1

HCID 31374DimethylacetamideSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 6-chloro-11H-benzo[e]pyrido[3,2-b][1,4]diazepine (822 mg, 3.58 mmol) and diisopropylethylamine (2 mL) in N,N-dimethylacetamide (25 mL) was added tert-butyl 4-(hydrazinecarbonyl)phenethylcarbamate (1.0 g, 3.58 mmol). The mixture was stirred at 80° C. for 24 hours then 100° C. for an additional 48 hours. The mixture was poured into ethyl acetate (150 mL) and washed with water (2×700 mL). The organic layer was dried over anhydrous magnesium sulfate and evaporated to dryness to give a brown foam. This residue was purified by silica gel chromatography eluting with ethyl acetate in hexanes (75-80%) to give a brown foam that was crystallized from dichloromethane to yield tert-butyl 4-(9H-benzo[f]pyrido[2,3-b][1,2,4]triazolo[4,3-d][1,4]diazepin-3-yl)phenethylcarbamate as off white crystals (717 mg). M.p.=145-148° C.; 400 MHz 1H NMR (CDCl3) δ: 8.21-8.17 (m, 2H), 7.44-7.37 (m, 3H), 7.24-7.16 (m, 3H), 7.0 (dd, J=1.6, 8.4 Hz, 2H), 6.82-6.79 (m, 1H), 6.38 (s, 1H), 4.55 (br.s, 1H), 3.42-3.37 (m, 2H), 2.84 (t, J=7.2 Hz, 2H), 1.44 (s, 9H). LCMS [M+H]: 455.

Workup

  1. wait100° C. for an additional 48 hours
  2. washwashed with water (2×700 mL)
  3. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  4. customevaporated to dryness
  5. customto give a brown foam
  6. customThis residue was purified by silica gel chromatography
  7. washeluting with ethyl acetate in hexanes (75-80%)
  8. customto give a brown foam that
  9. customwas crystallized from dichloromethane

Sources & evidence

ORD record
ord-930a2e582b1a484aa0e47a50066df76b
Source dataset
uspto-grants-2013_09
Patent number
US08541407B2

Reaction notes

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