Tetrahydrofuran → 4-({4-[(Trimethylsilyl)ethynyl]phenyl}ethynyl)aniline

HRID 1692528Notes

Reaction equation

HRID 1692528 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([C:8]#[C:9][Si:10]([CH3:13])([CH3:12])[CH3:11])=[CH:4][CH:3]=1.[C:14]([C:16]1[CH:21]=[CH:20][C:19]([NH2:22])=[CH:18][CH:17]=1)#[CH:15].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.O>[CH3:11][Si:10]([C:9]#[C:8][C:5]1[CH:6]=[CH:7][C:2]([C:15]#[C:14][C:16]2[CH:21]=[CH:20][C:19]([NH2:22])=[CH:18][CH:17]=2)=[CH:3][CH:4]=1)([CH3:13])[CH3:12]

Participants

7

Reactant 3

HCID 8028TetrahydrofuranHCID 37600254-EthynylanilineHCID 11808725(4-Iodophenylethynyl)trimethylsilane

Product 1

HCID 597475244-({4-[(Trimethylsilyl)ethynyl]phenyl}ethynyl)anilineYield 88.4%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
40 °C

Procedure

Following a general coupling procedure, (4-iodo-phenylethynyl)-trimethyl-silane (Maya et al., Chem. Mater., 2004, 16:2987-2997) (0.75 g, 2.50 mmol) was coupled to 4-ethynyl-phenylamine (Fan et al., J. Am. Chem. Soc., 2002, 124:5550) (0.35 g, 3.00 mmol) using PdCl2(PPh3)2 (0.09 g, 0.13 mmol), CuI (0.05 g, 0.25 mmol), TEA (3 mL), and THF (10 mL). The reaction was stirred at 40° C. overnight. The mixture was poured into H2O and extracted (3×) with CH2Cl2, dried using anhydrous MgSO4, and concentrated in vacuo. Column chromatography, silica gel (CH2Cl2) afforded 4-(4-trimethylsilanylethynyl-phenylethynyl)-phenylamine as a yellow solid (0.64 g). Following the general deprotection of TMS-protected alkynes, 4-(4-trimethylsilanylethynyl-phenylethynyl)-phenylamine (0.64 g, 2.21 mmol) was dissolved in a mixture of CH2Cl2 (15 mL), MeOH (15 mL), and K2CO3 (1.53 g, 11.05 mmol). The product 6, was afforded without additional purification as an orange solid (0.47 g, 87%, 2 steps). 1H NMR (400 MHz, (CD3)2CO) δ 7.45 (m, 4H), 7.25 (d, J=6.7 Hz, 2H), 6.68 (d, J=6.7 Hz, 2H), 5.09 (s, 2H), 3.77 (s, 1H).

Workup

  1. extractionextracted (3×) with CH2Cl2
  2. customdried
  3. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ae6dcf759c2246e8a1ef5920c3323761
Source dataset
uspto-grants-2012_04
Patent number
US08158203B2

Reaction notes

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