(4-BROMOPHENYLETHYNYL)TRIMETHYLSILANE

In a two neck rbf containing TEA (200 ml) was added 1-Bromo-4-iodobenzene 5 (24.00 g, 84.83 mmol) at rt under nitrogen. Themixture was stirred for 5 min followed by addition ofethynyltrimethylsilane 2 (13.19 ml, 93.31 mmol), Pd(PPh3)2Cl2(2.98 g, 4.24 mmol) and CuI (1.62 g, 8.48 mmol). The reaction mixturewas stirred for 30 min at the same temperature. The reactionmixture was evaporated in vaccum to remove excess of TEA followedby addition of 1 N HCl until the pH reached to 1. The mixturewas then extracted with EtOAc/water. The organic layer waswashed with brine and dried over anhydrous MgSO4. The solventwas evaporated and the residue was purified by column chromatography(Hexane) to give the desired compound 6 (21.00 g)as a white solid; Yield = 98percent; 1H NMR (CDCl3, 500 MHz): d 7.19–7.06 (4H, m, ArAH), 0.00 (9H, s, ASi(CH3)3); 13C NMR (CDCl3, 125 MHz): d 133.5, 131.6, 122.8, 122.3, 104.0, 95.7, 0.00.To an anhydrous triethylamine solution (30 mL), 4-iodo-bromobenzene(2.0 g, 7.07 mmol) was dissolved at room temperature.This solution was cooled in an ice bath, and Pd(PPh3)4 (0.20 g, 0.18 mmol) and CuI (34.28 mg, 0.18 mmol) were added. Cold trimethylsilylacetylene solution (1.1 mL, 0.76 g, 7.78 mmol) wasthen added in a dropwise manner. The mixture was stirred in anice bath for 1.5 h, and then saturated NH4Cl aqueous solution(30 mL) was added. The product was extracted with CH2Cl2(3 50 mL), and the organic phases were combined and dried overNa2SO4. Purification by chromatography on silica gel gave a whitesolid (1.73 g, 6.82 mmol, 96percent yield). 1H NMR (CDCl3): d 7.45–7.41(m, 2H), 7.33–7.30 (m, 2H), 0.25 (s, 9H).A mixture of 4-iodobromobenzene (2.01 g, 7.10 mmol), trimethylsilylacetylene (1.2 mL, 8.67 mmol), PdCl2(PPh3)2 (52 mg, 0.074 mmol), and CuI (15 mg, 0.079 mmol), NEt3 (5 mL) in THF (20 mL) was stirred at 25 °C. After stirring for 1.5 h, to the mixture was added aqueous 2 M HCl, and extracted with EtOAc (3 times). The organic phase was sequentially washed with brine, aqueous sat.NaHCO3, and brine, and dried with MgSO4. After concentration, the residue was purified with silicagel column chromatography (hexane to hexane/EtOAc = 8/2) to afford 4-(trimethylsilylethynyl)bromobenzene as colorless solids (1.71 g, 95percent). mp 56-59 °C (colorless plates); Rf: 0.65 (hexane); 1H NMR (CDCl3, 400 MHz): 0.06 (s, 9H), 7.13 (d, 2H, J = 8.5 Hz), 7.24 (d, 2H, J = 8.5 Hz); 13C NMR (CDCl3, 100 MHz):  -0.1, 95.6, 103.8, 122.1, 122.7, 131.5, 133.4; IR (KBr): vmax 2956, 2898, 2285, 2157, 1895, 1645, 1580, 1484, 1412, 1392, 1311, 1246, 1209, 1110, 1094, 1070, 1009, 844, 822 cm-1; HRMS (DART): [M+H]+ calcd for C11H13BrSi, 253.00481; found, 252.99518.To a mixture of 1-bromo-4-iodobenzene(1) (3.0 g, 10.06 mmol), dichlorobis(triphenylphosphine)palladium (II) (28 mg, 0.04 mmol), and copper iodide (18 mg, 0.09 mmol) in triethylamine (30 ml) was added trimethylsilylacetylene(1.7 ml, 11.94 mmol), and stirred at 48C for 2 hours. Solvent was evaporatedunder reduced pressure, and the residue was chromatographed on silica gel with hexaneto give 2 (2.42 g, 95percent) in a white solid. 1H NMR (CDCl3, 400 MHz): δ = 0.25 (s, 9H), 7.30(d, 2H), 7.40 (d, 2H). Anal. Calcd for C11H13BrSi: C, 52.17percent; H, 5.17percent. Found: C, 52.29percent; H, 5.08percent10.0 g of 1-bromo-4-iodobenzene, 400 mg of Pd (OAc) 2, 170 mg of CuI and 250 mg of PPh3 were placed in a 500 mL flask and an argon atmosphere was made. This mixture was diluted with 28.6 g of dry TEA. The mixture was bubbled with argon to remove oxygen and the temperature was lowered to 0 & lt; 0 & gt; C. 4.16 g of (trimethylsilyl) acetylene slowly putThe reaction mixture was stirred for 3 hours. The reaction was quenched with aqueous NH4Cl and extracted with CH2Cl2. The combined organic layers were dried over MgSO4, filtered and concentrated. 8.50 g of [(4-Bromophenyl) ethynyl] (trimethyl) silane was obtained through column chromatography (SiO2, Hexanes: EtOAc = 15: 1)Compound 76.1. ((4-Bromophenyl)ethynyl)trimethylsiIane. Into a 100-mL three neck round-bottom flask, which was maintained with an inert atmosphere of nitrogen, was placed a solution of l -bromo-4-iodobenzene (1.00 g, 3.53 mmol) in tetrahydrofuran/TEA(9: l) (30 mL). PdClCompound 76.1. ((4-Bromophenyl)ethynyl)trimethylsilane. 1-bromo-4-iodobenzene (200.0 g, 704.8 mmol), (1, 1 ‘-bis(diphenylphosphine)ferrocene)dichloropalladium(D) (25.8 g, 35.4 mmol), copper iodide (4.04 g, 21.2 mmol), triethylamine (295.6 ml, 2120 mmol), and tetrahydrofuran(1700 mE) were put in a 3 E round-bottomed flask under anitrogen atmosphere. Then, trimethyl silylacetylene (107.6 ml, 776.6 mmol) was added thereto in a dropwise fashion, and the mixture was stirred at room temperature for 3 hours. The reactant was filtered, and a solvent therein was removed. The resultant was purified through column chromatography to obtain an intermediate 1-11 (155.3 g, a yield:87percent).1-Bromo-4-iodobenzene (1a, 300 mg, 1.06 mmol), Pd(PPh34 (61.2 mg, 0.053 mmol), and CuI (20 mg, 0.11 mmol) were dissolved in 10 mL of triethylamine and trimethylsilyl acetylene (1b, 176 mL, 1.27 mmol) was added slowly at 0° C. Then, reaction mixture was stirred under N2 atmosphere for 5 h and trimethylamine was distilled off under vacuo. The residue obtained was taken up in ethyl acetate and washed with distilledwater and brine. The organic layer was next driedover anhydrous MgSO4 and evaporated in vacuo togive the crude product. Then the crude product was purified by flash column chromatography on silica gel to give ((4-bromophenyl)ethynyl)trimethylsilane (1) as awhite solid (192 mg, 71.5percent).11 1H NMR (400 MHz, CDCl3: 7.40 (d, 8.4 Hz, 2H), 7.30 (d, 8.4 Hz, 2H), 0.24 (s, 0.22 Hz, 9H).General procedure: A solution of Ar

Molecular Weight:253.21
Rotatable Bond Count:2
Exact Mass:251.99699
Monoisotopic Mass:251.99699
Heavy Atom Count:13
Complexity:220
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes