Hydrochloric Acid → HCID 59582214, compound

HRID 2061295Notes

Reaction equation

HRID 2061295 reaction equation
BrC1C=CC2N(C3CCCCO3)C3C(C=2C=1)=CC(Br)=CC=3.NC1C=CC=CC=1.[OH-].[K+].[C:31]1([NH:37][C:38]2[CH:39]=[CH:40][C:41]3[N:42](C4CCCCO4)[C:43]4[C:48]([C:49]=3[CH:50]=2)=[CH:47][C:46]([NH:51][C:52]2[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=2)=[CH:45][CH:44]=4)[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1.Cl>[Br-].C([N+](C)(C)C)CCCCCCCCCCCCCCC.C(OCC)(=O)C.C1COCC1.C1(C)C=CC=CC=1>[C:52]1([NH:51][C:46]2[CH:45]=[CH:44][C:43]3[NH:42][C:41]4[C:49]([C:48]=3[CH:47]=2)=[CH:50][C:38]([NH:37][C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)=[CH:39][CH:40]=4)[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1

Participants

10

Reactant 5

HCID 313Hydrochloric AcidHCID 6115AnilineHCID 14797Potassium HydroxideHCID 59582205HCID 59582205, compoundHCID 59582216HCID 59582216, compound

Product 1

HCID 59582214HCID 59582214, compoundYield 42%

Reagents, catalysts & solvents 4

HCID 5974Hexadecyltrimethylammonium BromideCatalystHCID 1140TolueneSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a dried flask under N2, were added 3,6-dibromo-9-(tetrahydro-2H-pyran-2-yl)-9H-carbazole (1) (37.5 g), aniline (25 mL), hexadecyltrimethylammonium bromide (430 mg), aqueous potassium hydroxide (68.6 g, 45% in water), toluene (1.2 L). The stirred mixture was purged with N2 for 15 min. Then to this mixture, were added Pd2 dba3 (4.12 g) and tri-tert-butylphosphine (2.97 g in anhydrous toluene). The reaction was heated to reflux overnight. The reaction was cooled down to room temperature, and anhydrous MgSO4 was added, and filtered through a layer of silica gel and celite. The solvent was removed and crude product was used for next reaction without purification. To a 2 L flask under N2, was added all the crude product of N3,N6-diphenyl-9-(tetrahydro-2H-pyran-2-yl)-9H-carbazole-3,6-diamine (2), THF (1 L), and concentrated HCl (20 mL). The reaction mixture was stirred for 2 h. The THF (700 mL) was removed by evaporation, and then poured into ice water, filtered to obtain the solid crude product. The solid was stirring in ethyl acetate (500 mL) for 2 h, and filtration gave the final product (13.7 g) in 42% yield for two steps. 1H NMR was consistent with the compound.

Workup

  1. customThe stirred mixture was purged with N2 for 15 min
  2. additionThen to this mixture, were added Pd2 dba3 (4.12 g) and tri-tert-butylphosphine (2.97 g in anhydrous toluene)
  3. temperatureThe reaction was heated
  4. temperatureto reflux overnight
  5. additionanhydrous MgSO4 was added
  6. filtrationfiltered through a layer of silica gel and celite
  7. customThe solvent was removed
  8. customcrude product was used for next reaction without purification
  9. customThe THF (700 mL) was removed by evaporation
  10. additionpoured into ice water
  11. filtrationfiltered
  12. customto obtain the solid crude product
  13. filtrationfiltration

Sources & evidence

ORD record
ord-46c95bb117f14214b908843eda6718bd
Source dataset
uspto-grants-2012_10
Patent number
US08283002B2

Reaction notes

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