Triethylamine → 5-(2-Aminophenylethynyl)-2,4-dimethoxybenzaldehyde

HRID 347356Notes

Reaction equation

HRID 347356 reaction equation
I[C:2]1[C:3]([O:12][CH3:13])=[CH:4][C:5]([O:10][CH3:11])=[C:6]([CH:9]=1)[CH:7]=[O:8].CCN(CC)CC.C[Si]([C:25]#[C:26][C:27]1[CH:33]=[CH:32][CH:31]=[CH:30][C:28]=1[NH2:29])(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[NH2:29][C:28]1[CH:30]=[CH:31][CH:32]=[CH:33][C:27]=1[C:26]#[C:25][C:2]1[C:3]([O:12][CH3:13])=[CH:4][C:5]([O:10][CH3:11])=[C:6]([CH:9]=1)[CH:7]=[O:8]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 2724141Tetrabutylammonium FluorideHCID 43779532-(2-(Trimethylsilyl)ethynyl)anilineHCID 142459555-Iodo-2,4-dimethoxybenzaldehyde

Product 1

HCID 161156205-(2-Aminophenylethynyl)-2,4-dimethoxybenzaldehydeYield 75.5%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

Ex-35C: To a solution of 5-iodo-2,4-dimethoxybenzaldehyde (Ex-35B, 11.7 g, 40 mmol) in 250 ml of THF, PdCl2(PPh3)2 (0.56 g, 0.8 mmol), CuI (0.3 g, 1.6 mmol), Et3N (6.06 g, 60 mmol), and 2-[(trimethylsilyl)ethynyl]aniline (7.92 g, 42 mmol) were added. The mixture was stirred to a homogeneous solution, and then TBAF (10.4 g, 40 mmol) was added. The reaction mixture was aged at room temperature for 4 h and then filtered. The filtrate was concentrated to about 50 ml, and the precipitate was filtered to give first portion of 5-(2-aminophenylethynyl)-2,4-dimethoxybenzaldehyde (8.5 g), as light yellow crystals. The filtrate was concentrated, and the residue was recrystallized from EtOAc/hexanes to give 1.85 g of additional product (total 10.35 g, 92%), mp 180–181° C. 1H-NMR (300 MHz, CDCl3) δ 10.30 (s, 1H), 7.99 (s, 1H), 7.36 (d, J=8 Hz, 1H), 7.11–7.17 (m, 1H), 6.69–6.75 (m, 2H), 6.46 (s, 1H), 4.41 (brs, 2H), 4.02 (s, 3H), 4.00 (s, 3H). HRMS Calcd. for C17H15NO3: 281.1052 (M+); Found: 281.1056. Anal. Calcd. for C17H15NO3: C, 72.58; H, 5.37; N, 4.98; Found: C, 72.74; H, 5.38; N, 4.93.

Workup

  1. filtrationfiltered
  2. concentrationThe filtrate was concentrated to about 50 ml
  3. filtrationthe precipitate was filtered

Sources & evidence

ORD record
ord-0d738922df4540e09c3299b480e8922b
Source dataset
uspto-grants-2007_02
Patent number
US07173129B2

Reaction notes

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