Benzyl (4-oxocyclohexyl)carbamate → (6-Cyano-2,3,4,9-tetrahydro-1H-carbazol-3-yl)-carbamic acid benzyl ester

HRID 545560Notes

Reaction equation

HRID 545560 reaction equation
Cl.[C:2]([C:4]1[CH:9]=[CH:8][C:7]([NH:10]N)=[CH:6][CH:5]=1)#[N:3].[CH2:12]([O:19][C:20](=[O:29])[NH:21][CH:22]1[CH2:27][CH2:26][C:25](=O)[CH2:24][CH2:23]1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>C(O)(=O)C>[CH2:12]([O:19][C:20](=[O:29])[NH:21][CH:22]1[CH2:23][C:24]2[C:8]3[C:7](=[CH:6][CH:5]=[C:4]([C:2]#[N:3])[CH:9]=3)[NH:10][C:25]=2[CH2:26][CH2:27]1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

4

Reactant 2

HCID 14615292Benzyl (4-oxocyclohexyl)carbamateHCID 162129624-Cyanophenylhydrazine Hydrochloride

Product 1

HCID 57431676(6-Cyano-2,3,4,9-tetrahydro-1H-carbazol-3-yl)-carbamic acid benzyl esterYield 69.3%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Combine 4-cyanophenylhydrazine hydrochloride (27.4 g, 162 mmol) and (4-oxo-cyclohexyl)-carbamic acid benzyl ester (Preparation 42) (40.0 g, 162 mmol) in acetic acid (800 mL). Heat the reaction to 90° C. overnight, then cool to room temperature and concentrate under reduced pressure. Triturate the residue in dichloromethane and discard the filter cake. Concentrate the filtrate under reduced pressure. Purify the resulting residue by flash chromatography (silica gel, 9:1 chloroform:acetone). Recrystillize the resulting material from benzene to provide 38.8 g (69%) of the title compound. m.p.=141-143° C.; mass spectrum (m/e): 344 [C21H19N3O2−1]−; 1H NMR (300 MHz, CDCl3): δ 8.15 (s, 1H), 7.73 (s, 1H), 7.29-7.38 (m, 7H), 5.12 (s, 2H), 4.89-4.92 (m, 1H), 4.18 (m, 1H), 3.09 (dd, J=5.0, 15.5 Hz, 1H), 2.78-2.91 (m, 2H), 2.59 (dd, J=7.0, 15.5 Hz, 1H), 2.07-2.17 (m, 1H), 1.93-2.05 (m, 1H).

Workup

  1. temperatureHeat
  2. customthe reaction to 90° C. overnight
  3. concentrationconcentrate under reduced pressure
  4. customTriturate the residue in dichloromethane
  5. concentrationConcentrate the filtrate under reduced pressure
  6. customPurify the resulting residue by flash chromatography (silica gel, 9:1 chloroform:acetone)

Sources & evidence

ORD record
ord-91ab0a15cb1d48cb9cdba8098bdaefe1
Source dataset
uspto-grants-2011_05
Patent number
US07935722B2

Reaction notes

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