Dimethylformamide → 9-Benzyl-3-formylcarbazole

HRID 659614Notes

Reaction equation

HRID 659614 reaction equation
CN(C)[CH:3]=[O:4].O=P(Cl)(Cl)Cl.[CH2:11]([N:18]1[C:30]2[CH:29]=[CH:28][CH:27]=[CH:26][C:25]=2[C:24]2[C:19]1=[CH:20][CH:21]=[CH:22][CH:23]=2)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>CCOC(C)=O>[CH2:11]([N:18]1[C:19]2[CH:20]=[CH:21][C:22]([CH:3]=[O:4])=[CH:23][C:24]=2[C:25]2[C:30]1=[CH:29][CH:28]=[CH:27][CH:26]=2)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 24813Phosphorus oxychlorideHCID 146485N-Benzylcarbazole

Product 1

HCID 30915349-Benzyl-3-formylcarbazoleYield 36.3%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A 50-mL 3-necked round-bottomed flask was charged with N,N-dimethylformamide (400 mg, 5.42 mmol, 2.80 equiv, 99%). To this, POCl3 (700 mg, 4.56 mmol, 2.40 equiv, 99%) was added drop wise with stirring at 0° C. and allowed to stir at room temperature for 1 hour. To this mixture was added 9-benzyl-9H-carbazole (500 mg, 1.93 mmol, 1.00 equiv, 99%) in small portions at 45° C. over 5 minutes. Then, the temperature was raised to 95° C. in an oil bath and allowed to stir for 18 hours. The progress was monitored by TLC (EtOAc:PE=1:4). Upon completion, the reaction mixture was cooled down to room temperature and quenched with water (20 mL). The resulting mixture was allowed to stir for an additional 4 hours at room temperature. The solids were collected by filtration and dried to afford 9-benzyl-9H-carbazole-3-carbaldehyde as green solid (200 mg, 36.1%). LCMS: [M+H]+: 286

Workup

  1. stirringto stir at room temperature for 1 hour
  2. temperatureThen, the temperature was raised to 95° C. in an oil bath
  3. stirringto stir for 18 hours
  4. temperatureUpon completion, the reaction mixture was cooled down to room temperature
  5. customquenched with water (20 mL)
  6. stirringto stir for an additional 4 hours at room temperature
  7. filtrationThe solids were collected by filtration
  8. customdried

Sources & evidence

ORD record
ord-51d5def88816466c93d27c67a79c1724
Source dataset
uspto-grants-2011_12
Patent number
US08080566B1

Reaction notes

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