Nitric Acid → 3,6-Dibromo-1-nitro-9H-carbazole

HRID 359665Notes

Reaction equation

HRID 359665 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[NH:6][C:7]3[C:12]([C:13]=2[CH:14]=1)=[CH:11][C:10]([Br:15])=[CH:9][CH:8]=3.[N+:16]([O-])([OH:18])=[O:17]>C(O)(=O)C>[Br:15][C:10]1[CH:9]=[C:8]([N+:16]([O-:18])=[O:17])[C:7]2[NH:6][C:5]3[C:13]([C:12]=2[CH:11]=1)=[CH:14][C:2]([Br:1])=[CH:3][CH:4]=3

Participants

4

Reactant 2

HCID 944Nitric AcidHCID 2748743,6-Dibromocarbazole

Product 1

HCID 2217653,6-Dibromo-1-nitro-9H-carbazole

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
0 °C

Procedure

Acetic acid (600 ml) and 3,6-dibromocarbazole (45 g) was placed into a one liter three-necked RB flask equipped with a reflux condenser, mechanical stirrer, and heating mantle. The stirred solution was heated to reflux at which time a solution of nitric acid (10 ml, density 1.4 g/cc, 0.156 mole in 100 ml of acetic acid) was added over a period of 30 minutes. After 2/3 of the nitrating mixture was added, a flocculent yellow precipitate deposited. The remainder of the nitrating mixture was added and the whole refluxed gently for one hour, cooled to 0° C. in an ice bath and filtered. The crude yellow precipitate softens at 232° C. and melts at 243°-246° C. The crude product was recrystallized from boiling acetonitrile to give yellow crystals with m.p. 252°-256° C. (uncovered), 256°-260° C. (covered). [H. Lindemann & F. Muhlhaus, Ber., 58, 2371 (1925) report a m.p. of 260° C. for the product].

Workup

  1. customequipped with a reflux condenser, mechanical stirrer
  2. temperatureheating mantle
  3. temperatureThe stirred solution was heated
  4. additionwas added over a period of 30 minutes
  5. additionAfter 2/3 of the nitrating mixture was added
  6. additionThe remainder of the nitrating mixture was added
  7. temperaturethe whole refluxed gently for one hour
  8. filtrationfiltered
  9. customsoftens at 232° C.
  10. customThe crude product was recrystallized
  11. customto give yellow crystals with m.p. 252°-256° C. (uncovered), 256°-260° C. (covered)

Sources & evidence

ORD record
ord-b118804ae30249a39a00215ac474f41f
Source dataset
uspto-grants-1991_03
Patent number
US05002856

Reaction notes

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