4′‐Hydroxy‐[1,1′‐biphenyl]‐2‐carbonitrile

Abstract

[137863-68-4] C13H9NO (MW 195.22) InChI = 1S/C13H9NO/c14-9-11-3-1-2-4-13(11)10-5-7-12(15)8-6-10/h1-8,15H InChIKey = HBPAPDGVCPVONJ-UHFFFAOYSA-N (para-selective directing group [DG]) Physical Appearance: colorless crystalline solid. Physical Data: 150–152 °C (MP). Solubility: soluble in various polar protic and aprotic solvents such as methanol, isopropanol, hexafluoroisopropanol (HFIP), dichloromethane, dichloroethane, chloroform, ethyl acetate, acetonitrile, and acetone. Analytical Data: 1H NMR (400 MHz, CDCl3) δ 7.75 (dd, J = 7.8, 1.4 Hz, 1H), 7.62 (td, J = 7.7, 1.4 Hz, 1H), 7.49 (dd, J = 7.9, 1.2 Hz, 1H), 7.43–7.48 (m, 2H), 7.40 (td, J = 7.6, 1.3 Hz, 1H), 6.99–6.91 (m, 2H), 5.63 (d, J = 6.3 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 111.0, 115.9, 119.2, 127.3, 130.1, 130.4, 130.7, 133.1, 134.0, 145.5, 156.7. HRMS (m/z): [M + Na+] calculated for C13H9NNaO, 218.0582; found, 218.0590. IR: 3384, 3190, 2231, 1709, 1663, 1613, 1520, 1480, 1448, 1279, 1174, 832, 758 cm−1. Preparative Method:1 a clean, oven-dried screw cap reaction tube with previously placed magnetic stir bar was charged with 2-cyanophenyl boronic acid (1.5 equiv, 438 mg for 2 mmol), palladium acetate (2 mol%, 9 mg for 2 mmol), SPhos (4 mol%, 33 mg for 2 mmol), K3PO4 (2 equiv, 849 mg for 2 mmol), and 4-bromophenol (2 mmol, 354 mg). The cap was fitted with a rubber septum, and the reaction tube was evacuated and backfilled with nitrogen, and this sequence was repeated three additional times. Now under the positive flow of nitrogen, 6 mL THF was added to the reaction mixture. The several reactions were carried out in different reaction tubes (2 mmol/reaction tube). The reaction mixture was vigorously stirred (600 rpm on Heidolph MR Hei-Standard stirrer) on an oil bath of 100 °C temperature for 24 h. Now the reaction mixture was dried using rotary evaporator. The reaction mixture was extracted thrice with ethyl acetate (3 × 20 mL) and brine solution (3 × 10 mL). The organic layer was collected and dried over anhydrous Na2SO4. After filtration and evaporation of the solvent, the crude mixture was purified by column chromatography using neutral alumina and petroleum-ether/ethyl acetate (85/15, v/v) as the eluent. The desired 4′-hydroxy-[1,1′-biphenyl]-2-carbonitrile was isolated in 43% yield. Handling, Storage, and Precautions: the title compound is stable under normal atmospheric conditions and does not undergo decomposition over a period of time when stored in a sealed container. It is safe to handle, without any risk of burns or inflammation.