Aniline → HCID 11220504, compound

HRID 1824727Notes

Reaction equation

HRID 1824727 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:8][C:9]1(C)[C:35]2[C:30](=[C:31](P(C3C=CC=CC=3)C3C=CC=CC=3)C=[CH:33][CH:34]=2)O[C:11]2[C:12](P(C3C=CC=CC=3)C3C=CC=CC=3)=[CH:13][CH:14]=[CH:15][C:10]1=2.[C:50]([O-:53])([O-])=O.[Cs+].[Cs+].[NH3:56].O>C1(C)C=CC=CC=1.CCOC(C)=O.C(Cl)Cl.CO.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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:2]1([NH:1][C:13]2[CH:14]=[CH:15][C:50]3[O:53][C:9]4([CH2:8][N:56]5[CH2:31][CH2:30][CH:35]4[CH2:34][CH2:33]5)[CH2:10][C:11]=3[CH:12]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

10

Reactant 4

HCID 6115AnilineHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 12896473Azane;hydrate

Product 1

HCID 11220504HCID 11220504, compound

Reagents, catalysts & solvents 5

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 887MethanolSolventHCID 1140TolueneSolventHCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

The product of 1E (200 mg, 0.68 mmol) was coupled with aniline (Aldrich, 130 mg, 1.40 mmol) catalyzed by Pd2(dba)3 (Strem Chemicals, 12.4 mg, 0.014 mmol) and Xantphos (Strem Chemicals, 24.3 mg, 0.042 mmol) with Cs2CO3 (Aldrich, 460 mg, 1.4 mmol) in toluene (Aldrich, anhydrous, 10 mL) at 110° C. for 20 h. The reaction was monitored with TLC. After the reaction was complete, it was diluted with EtOAc (30 mL) and washed with brine (2×5 mL). The organic solution was concentrated and the title compound was purified by chromatography (SiO2, CH2Cl2:MeOH:NH3.H2O, 90:10:2, Rf. 0.20) as oil (120 mg, 58% yield). 1H NMR (MeOH-d4, 300 MHz) δ 1.52–1.63 (m, 1H), 1.73–1.85 (m, 2H), 1.99–2.06 (m, 1H), 2.13–2.25 (m, 1H), 2.84–3.43 (m, 8H), 6.63 (d, J=8.6 Hz, 1H), 6.70 (tt, J=7.1, 1.2 Hz, 1H), 6.80–7.90 (m, 2H), 6.96–6.99 (m, 1H), 7.06–7.16 (m, 2H) ppm. MS (DCl/NH3) m/z 307 (M+H)+.

Workup

  1. washwashed with brine (2×5 mL)
  2. concentrationThe organic solution was concentrated

Sources & evidence

ORD record
ord-80c464278ce74b0eb5514aeb14e0cb30
Source dataset
uspto-grants-2006_05
Patent number
US07045530B2

Reaction notes

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