Carbazole → HCID 66780455, compound

HRID 572955Notes

Reaction equation

HRID 572955 reaction equation
[CH:1]1[C:13]2[NH:12][C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]=2[CH:4]=[CH:3][CH:2]=1.[C:14](Br)([CH2:17][C:18]([CH3:21])([CH3:20])[CH3:19])([CH3:16])[CH3:15]>[N+](C)([O-])=O.C1(C)C=CC=CC=1.[Cl-].[Cl-].[Zn+2]>[CH3:19][C:18]([CH3:21])([CH2:17][CH:14]([CH3:16])[CH3:15])[CH2:20][C:3]1[CH:2]=[CH:1][C:13]2[NH:12][C:11]3[C:6]([C:5]=2[CH:4]=1)=[CH:7][C:8]([CH2:19][C:18]([CH3:21])([CH3:20])[CH2:17][CH:14]([CH3:16])[CH3:15])=[CH:9][CH:10]=3

Participants

6

Reactant 2

HCID 6854CarbazoleHCID 11435470Pentane, 2-bromo-2,4,4-trimethyl-

Product 1

HCID 66780455HCID 66780455, compound

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 1140TolueneSolventHCID 6375NitromethaneSolvent

Procedure

ZnCl2 (36.8 g, 276 mmol) and carbazole (21.0 g, 126 mmol) are suspended in 600 mL nitromethane in a 1 qt jar in a glove-box. The t-octyl bromide (53.4 g, 276 mmol) is added dropwise to the gray-green suspension via addition funnel. The mixture turns into a black solution during the addition. The solution is allowed to stir at room temperature for two hours and then poured into 500 mL ice water. The product is extracted out of the mixture with 500 mL and 250 mL CH2Cl2. The combined organic portions are dried with MgSO4, filtered and rotovapped to yield a dark residue. This residue is taken up in 200 mL toluene, passed through a plug of silica, and washed through with 150 mL toluene. The yellow solution is reduced to a solid on the rotovap. This material is recrystallized from 100 mL hexane at −13° C. 27 g (55%) of white crystals are collected. The crystallization only moderately improved the purity of the product. 1H NMR (CDCl3): δ 8.02 (d, JH-H=1.6 Hz, 2H), 7.80 (br s, 1H, NH), 7.42 (dd, JH-H=8.6, 1.8 Hz, 2H), 7.29 (d, JH-H=8.5 Hz, 2H), 1.83 (s, 4H, CH2), 1.49 (s, 12H, CMe2), 0.72 (s, 18H, CMe3).

Workup

  1. additionThe mixture turns into a black solution during the addition
  2. extractionThe product is extracted out of the mixture with 500 mL and 250 mL CH2Cl2
  3. dry with materialThe combined organic portions are dried with MgSO4
  4. filtrationfiltered
  5. customto yield a dark residue
  6. washwashed through with 150 mL toluene
  7. customThis material is recrystallized from 100 mL hexane at −13° C
  8. custom27 g (55%) of white crystals are collected
  9. customThe crystallization

Sources & evidence

ORD record
ord-d6d47f43c6664eb0b1819f204c75ad96
Source dataset
uspto-grants-2015_05
Patent number
US09029487B2

Reaction notes

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