Ethyl Acetate → HCID 86644269, compound

HRID 518908Notes

Reaction equation

HRID 518908 reaction equation
[C:1](=[N:14][NH2:15])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.Cl[C:17]([O:19][CH2:20][C:21]1C=CC([N+:27]([O-])=O)=CC=1)=[O:18].CC[O:32][C:33](C)=[O:34].CC[N:38]([CH:42](C)C)C(C)C>C(Cl)Cl>[CH2:20]([O:19][C:17](=[O:18])[CH2:42][NH:38][C:1](=[O:32])[NH:14][NH2:15])[CH3:21].[C:1](=[N:14][NH:15][C:33]([NH2:27])=[O:34])([C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 782054-Nitrobenzyl chloroformateHCID 79304Diphenylmethylidenehydrazine2×HCID 81531Diisopropylethylamine

Product 1

HCID 86644269HCID 86644269, compoundYield 60%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Benzophenone hydrazone (500 mg, 2.5 mmol) in DCM (5 mL) was added dropwise over 15 min to a solution of p-nitrobenzyl chloroformate (600 mg, 3 mmol) in DCM (5 mL) at 0° C. The reaction mixture was stirred at room temperature under argon for an additional 1.5 h, until TLC, [(2:1 Hex:EtOAc), Rf (benzophenone hydrazone): 0.45 and Rf (31): 0.7] indicated complete consumption of the starting material. To this mixture was added dropwise DIPEA (400 μL, 4.6 mmol) and the suspension was stirred for an additional 3 h at room temperature, (22° C.) under argon. The reaction mixture was diluted in DCM (60 mL) and extracted several times with NaHCO3 (8×30 mL). The organic phase was dried over MgSO4, concerntrated in-vacuo and purified by flash chromatography using 2:1 Hexane:EtOAc [Rf (51): 0.25] to yield a white solid (0.5 g, 60%). 1H NMR (CDCl3) δ: 1.19 (t, J=7 Hz, 3H), 4.02 (d, J=5.6 Hz, 2H), 4.13 (q, J=7 Hz, 2H), 6.78 (t, J=5.5 Hz, 1H), 7.1-7.4 (m, 10H), 7.61 (s, 1H); 13C NMR (CDCl3) δ: 13.8, 41.4, 61.0, 126.8, 127.8, 127.9, 128.1, 129.0, 129.1, 129.36, 129.43, 129.5, 131.4, 136.5, 148.2, 151.0, 154.9, 170.0; LCMS (ESI) Calcd. for C18H19N3O3, M+: 325.4. found (M+H)+326.

Workup

  1. customconsumption of the starting material
  2. custom(22° C.)
  3. extractionextracted several times with NaHCO3 (8×30 mL)
  4. dry with materialThe organic phase was dried over MgSO4
  5. custompurified by flash chromatography

Sources & evidence

ORD record
ord-27c750d3b19644fbbaeace978b47abbd
Source dataset
uspto-grants-2015_08
Patent number
US09115171B2

Reaction notes

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