1-Naphthylamine → N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amine

HRID 2361204Notes

Reaction equation

HRID 2361204 reaction equation
I[C:2]1[CH:3]=[CH:4][C:5]2[N:6]([C:15]3[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=3)[C:7]3[C:12]([C:13]=2[CH:14]=1)=[CH:11][CH:10]=[CH:9][CH:8]=3.[NH2:21][C:22]1[C:31]2[C:26](=[CH:27][CH:28]=[CH:29][CH:30]=2)[CH:25]=[CH:24][CH:23]=1.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C.C(O[Na])(C)(C)C>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].C1(C)C=CC=CC=1.C1(C)C(C)=CC=CC=1>[C:22]1([NH:21][C:2]2[CH:3]=[CH:4][C:5]3[N:6]([C:15]4[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=4)[C:7]4[C:12]([C:13]=3[CH:14]=2)=[CH:11][CH:10]=[CH:9][CH:8]=4)[C:31]2[C:26](=[CH:27][CH:28]=[CH:29][CH:30]=2)[CH:25]=[CH:24][CH:23]=1

Participants

8

Reactant 4

HCID 86401-NaphthylamineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 118107403-Iodo-9-phenylcarbazoleHCID 178418730sodium 2-methylpropan-2-olate

Product 1

HCID 59132882N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amineYield 79%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolventHCID 7237O-XyleneSolvent

Conditions

Temperature
90 °C

Procedure

Under nitrogen, 12 mL of dehydration xylene was added to a mixture of 3.7 g (10 mmol) of 3-iodo-9-phenylcarbazole, 1.6 g (5 mmol) of 1-aminonaphthalen, 60 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium(0), 200 μL (0.5 mmol) of tri(t-butyl)phosphine (49 wt % hexane solution), 3 g (30 mmol) of t-butoxysodium (abbreviation: t-BuONa). This was stirred while heating at 90° C. under a nitrogen atmosphere for 7 hours. After the termination of the reaction, this suspension was added with about 200 mL of hot toluene and was filtered through florisil®, alumina, and celite. The obtained filtrate was concentrated and this residue was separated by silica gel column chromatography (toluene:hexane=1:1). When an obtained solid was recrystallized with a mixture of ethyl acetate and hexane, 1.5 g of 3-[N-(1-naphthyl)amino]-9-phenylcarbazole (PCN) that was a target substance and was cream-colored powder was obtained in a yield of 79% (Synthesis Scheme (g-1)).

Workup

  1. customAfter the termination of the reaction
  2. filtrationwas filtered through florisil®, alumina, and celite
  3. concentrationThe obtained filtrate was concentrated
  4. customthis residue was separated by silica gel column chromatography (toluene:hexane=1:1)
  5. customWhen an obtained solid was recrystallized with a mixture of ethyl acetate and hexane, 1.5 g of 3-[N-(1-naphthyl)amino]-9-phenylcarbazole (PCN) that
  6. customwas obtained in a yield of 79% (Synthesis Scheme (g-1))

Sources & evidence

ORD record
ord-dfb7ccf6abd1414dbc18e28aa96edc65
Source dataset
uspto-grants-2014_04
Patent number
US08686628B2

Reaction notes

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