Pyridine → HCID 86634058, compound

HRID 1041589Notes

Reaction equation

HRID 1041589 reaction equation
[CH3:1][C:2]1([CH3:16])[CH2:8][CH2:7][CH2:6][NH:5][C:4]2[CH:9]=[C:10]([N+:13]([O-:15])=[O:14])[CH:11]=[CH:12][C:3]1=2.N1C=CC=CC=1.Cl[C:24]([O:26][C:27]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][CH:28]=1)=[O:25]>CN(C)C1C=CN=CC=1.ClCCCl>[N+:33]([C:30]1[CH:29]=[CH:28][C:27]([O:26][C:24]([N:5]2[CH2:6][CH2:7][CH2:8][C:2]([CH3:16])([CH3:1])[C:3]3[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[CH:9][C:4]2=3)=[O:25])=[CH:32][CH:31]=1)([O-:35])=[O:34]

Participants

6

Reactant 3

HCID 1049PyridineHCID 821294-Nitrophenyl chloroformateHCID 574702565,5-dimethyl-8-nitro-2,3,4,5-tetrahydro-1H-benzo[b]azepine

Product 1

HCID 86634058HCID 86634058, compoundYield 46%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 111,2-DichloroethaneSolvent

Procedure

5,5-Dimethyl-8-nitro-2,3,4,5-tetrahydro-1H-benzo[b]azepine (0.797 g, 3.62 mmol), Pyridine (0.310 mL, 3.83 mmol) and 4-Dimethylaminopyridine (21 mg, 0.17 mmol) were dissolved in anhydrous 1,2-Dichloroethane (5.0 mL) before adding p-Nitrophenyl Chloroformate (0.541 g, 2.68 mmol). The reaction was stirred at room temperature for 41 hours and then concentrated under reduced pressure. The residue was purified by normal phase chromatography to yield an off-white solid, 5,5-Dimethyl-8-nitro-2,3,4,5-tetrahydro-benzo[b]azepine-1-carboxylic acid 4-nitro-phenyl ester (0.475 g, 46%). LCMS: m/z=386.07 (M+H+). 1H NMR (400 MHz, CDCl3) δ 8.21 (m, 4H), 7.65 (d, 1H, J=8.8 Hz), 7.42 (m, 1H), 7.23 (m, 1H), 4.53 (m, 1H), 2.87 (m, 1H), 2.32 (m, 1H), 1.69 (m, 5H), 1.34 (m, 4H).

Workup

  1. concentrationconcentrated under reduced pressure
  2. customThe residue was purified by normal phase chromatography

Sources & evidence

ORD record
ord-e13b4b7a59dd4d0485620dcca641cdc8
Source dataset
uspto-grants-2013_10
Patent number
US08552186B2

Reaction notes

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