(XYL)2P(O)H

1-Bromo-3, 5-dimethylbenzene (129.5 g, 3.5 equiv) was slowly added to a suspension of Mg turnings (17.0 g, 3.5 equiv) in THF (770 mL) while the internal temperature was maintained at 40–50 °C. The mixture was stirred at 40–50 °C for 1 h then cooled to 0 °C. (EtO)2POH (27.7 g, 0.200 mol) was added over 30 min, and the mixture was stirred at 0 °C for 1 h. The reaction was quenched with 6 M aq HCl (260 mL) and the mixture was extracted with CH2Cl2 (260 ×3 mL) and washed with H2O (130 × 2 mL). After concentration in vacuo, the residue was purified by chromatography on silica gel to give the title compound (49.7 g, 96percent) as a pale yellow solid.Bis(m-xylyl)phosphine oxide [1 87344-92-9].It was prepared according to a modified procedure.6 Under argon, finely ground LiCI (1.59 g, 37.5 mmol) was dissolved in dry THF(75 mL) in a 250-mL Schlenk flask. Magnesium turnings (0.73 g, 30.0 mmol) were added to this solution, followed by addition ofdiisobutylaluminum hydride (0.30 mL, 1—M in cyclohexane). The mixture was stirred for 5 mm at RT, followed by addition of 1-bromo-3, 5- dimethylbenzene (5.55g, 30.0 mmol). The stirring was continued for another 6 h at RT until all magnesium turnings were consumed. The resulting solution was cooled to -10°C in a salt/ice bath, followed by the addition of HP(O)(OEt)2 (1.38 g, 10.0 mmol) in THF (2.0 mL). The mixture was allowed to warm up to RT and the stirring was continued for 18 h. The reaction was quenched by a saturated aqueous NH4CI solution (100 mL), followed by extraction with EtOAc (100 mL x 2). The organic extracts were combined and dried over MgSO4, and concentrated on a rotary evaporator. Theresidue was purified by flash chromatography (hexane to 1:2 EtOAc/hexane), which afforded2.35 g (90percent) of the product as white powder.1H NMR (400 MHz, CDCI3): 7.95 (d, J 478.9 Hz, 1H), 7.31 (d, J = 14.2 Hz, 4H), 7.18(s, 2H), 2.35 (s, 12H).31P{1H} NMR (162 MHz, CDCI3): 22.6 (s).Under an argon atmosphere, a solution of magnesium (25 g, 0.95 equivalent) and a small amount of iodine in THF (250 mL) was stirred at room temperature for 1 hr. 5-Bromo-m-xylene (200 g, 1.08 moL) was added at 48°C, and the mixture was stirred at 5°C for 1 hr. Diethyl phosphite (78.3 g, 0.52 equivalent) was added at 5°C, and the mixture was stirred at 5°C for 2 hrs. Water (200 mL) was added at 3°C, and toluene (200 mL) and 6M-HCl (160 mL) were added. The mixture was stirred at room temperature for 30 min. The reaction mixture was partitioned, and the organic layer was washed successively with water (100 mL), 5percent aqueous NaHCO3 solution (100 mL) and 5percent aqueous NaCl solution (100 mL). The organic layer was dried over anhydrous magnesium sulfate and filtered by gravity. The filtrate was concentrated under reduced pressure and the residue was recrystallized from diisopropyl ether-heptane to give the title compound (43.3 g, white crystals). yield 33.3percent.Under a nitrogen stream, a solution of magnesium (3.28 g, 4.01 equivalents), a small amount of iodine and 1, 2-dibromoethane in THF (10 mL) was stirred at room temperature for 1.5 hrs. A solution of 5-bromo-m-xylene (25.2 g, 4.05 equivalents) in THF (100 mL) was added at 25°C, and the mixture was stirred at 40°C for 40 min. A solution of diethyl phosphite (4.64 g, 33.6 mmol) in THF (5 mL) was added at -33°C, and the mixture was stirred at 0°C for 30 min. Water (30 mL) was added at 3°C, and 6M-HCl (20 mL) and toluene (50 mL) were added. The mixture was stirred at room temperature for 30 min. The reaction mixture was partitioned, and the organic layer was washed with 10percent aqueous NaHCO3 solution (30 mL), and the organic layer was concentrated under reduced pressure. The residue was recrystallized from heptane and dried (reduced pressure, 50°C) to give the title compound (6.80 g, white powder). yield 78.3percent. melting point: 82.4°C.1H-NMR (300MHz, CDCl3, TMS) δ: 2.35 (s, 12H), 7.18 (s, 2H), 7.28 (s, 2H), 7.33 (s, 2H), 7.94 (d, 1H, JH-P = 477.0 Hz).31P-NMR (121MHz, CDCl3, 85percentH3PO4) δ: 23.89 (d, quint, JH-P = 477.1 Hz, JHCC-P = 13.7 Hz).

suzuki reaction

Molecular Weight:257.29
XLogP3:3.9
Hydrogen Bond Acceptor Count:1
Rotatable Bond Count:2
Exact Mass:257.109527191
Monoisotopic Mass:257.109527191
Topological Polar Surface Area:17.1
Heavy Atom Count:18
Formal Charge:1
Complexity:254
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes