N-Methylaniline → HCID 135405316, compound

HRID 2220770Notes

Reaction equation

HRID 2220770 reaction equation
Br[C:2]1[C:3]2[NH:7][C:6]([C:8]([C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)=[C:9]3[N:31]=[C:12]([CH:13]=[C:14]4[NH:30][C:17](=[C:18]([C:24]5[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=5)[C:19]5[CH:20]=[CH:21][C:22]=1[N:23]=5)[CH:16]=[CH:15]4)[CH:11]=[CH:10]3)=[CH:5][CH:4]=2.[CH3:38][NH:39][C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1.C1C=CC(P(C2C(OC3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=CC=3)=CC=CC=2)C2C=CC=CC=2)=CC=1.P.C(=O)([O-])[O-].[Cs+].[Cs+]>C1COCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.[Pd].C(OCC)(=O)C>[CH3:38][N:39]([C:2]1[C:3]2[NH:7][C:6]([C:8]([C:32]3[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=3)=[C:9]3[N:31]=[C:12]([CH:13]=[C:14]4[NH:30][C:17](=[C:18]([C:24]5[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=5)[C:19]5[CH:20]=[CH:21][C:22]=1[N:23]=5)[CH:16]=[CH:15]4)[CH:11]=[CH:10]3)=[CH:5][CH:4]=2)[C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1

Participants

10

Reactant 5

HCID 7515N-MethylanilineHCID 10796Cesium carbonateHCID 24404PhosphineHCID 4285986Bis[2-(diphenylphosphino)phenyl] etherHCID 173154257HCID 173154257, compound

Product 1

HCID 135405316HCID 135405316, compound

Reagents, catalysts & solvents 4

HCID 23938PalladiumCatalystHCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

The general procedure was used to couple 5-bromo-10,20-diphenylporphyrin (54 mg, 0.10 mmol) with N-methylaniline (40 μL, 0.36 mmol), using palladium acetate (1.1 mg, 0.005 mmol) as the palladium precursor, DPEphos (4.0 mg, 0.0075 mmol) as the phosphine ligand and cesium carbonate (45.6 mg, 0.014 mmol) as the base. The reaction was conducted in THF (5 mL) at 68° C. for 16 h. The title compound was isolated by flash column chromatography (silica gel, ethyl acetate:hexanes (v)=1:4) as purple solids (53 mg, 94%). 1H NMR (300 MHz, CDCl3): δ 10.18 (s, 1H), 9.30 (d, J=4.8 Hz, 2H), 9.19 (d, J=4.8 Hz, 2H), 9.00 (d, J=4.8 Hz, 2H), 8.90 (d, J=4.8 Hz, 2H), 8.23 (m, 4H), 7.78 (m, 6H), 7.19 (broad, 2H), 6.73 (broad, 3H), 4.26 (s, 3H), −2.82 (s, 2H). 13C NMR (75 MHz, CDCl3): δ 154.9, 141.6, 134.9, 131.9, 131.7, 131.6, 129.6, 129.1, 128.0, 127.2, 124.2, 119.8, 116.9, 113.9, 105.8, 45.5. IR (film, cm−1): 3303, 3055, 3026, 2875, 2810, 1596, 1498, 1351, 1113, 971, 796, 731. UV-vis (CHCl3, λmax, nm): 410, 512, 548, 592. HRMS-EI ([M]+): C39H29N5, 567.2423; found: 567.2419 with an isotope distribution pattern that is same as the calculated one.

Sources & evidence

ORD record
ord-485f12a2730144a4b3325c40b5ac6fd0
Source dataset
uspto-grants-2008_08
Patent number
US07417142B2

Reaction notes

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