3,5-Bis(methoxycarbonyl)phenylboronic acid pinacol ester

5-bromo-1, 3-benzenedicarboxylic acid dimethyl ester (5. 4 g, 19.8 mmol), boronic acid pinacol ester (6.0 g, (7.5 g, 57.2 mmol), placed in 250 mL three-necked flask, add anhydrous 1, 4-dioxane (50 mL) as solvent, protected by N2, 0 • 5 h Pd (dppf) 2C12 ( • 2 g, 0 • 27 mmol), the temperature was raised to 100 ° C for 12 h, the temperature dropped to room temperature and the excess of 1, 4-dioxane was distilled off. H2O (20 mL ), Extracted with ethyl acetate (30 mL) and extracted three times. The organic phase was collected and dried over anhydrous Na2SO3. The filtrate was evaporated to dryness to give the crude product. The crude product was purified by silica gel column chromatography (eluent: petroleum ether / acetic acid Ethyl ester = 94/6) to afford white powder B (4.59 g) in 72percent yield.Under nitrogen, a solution of 2, 4, 6-tris(4-bromophenyl)-1, 3, 5-triazine (3a, 803 mg, 1.47 mmol) [20], dimethyl 5-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-isophthalate (4, 1.69 g, 5.28 mmol), potassium acetate (1.30 g, 13.2 mmol), and 1, 1'-bis(diphenylphosphine)ferrocene-palladium(II) chloride (120 mg, 164 mol) in a 10:1 mixture (90 mL) of 1, 4-dioxane and water was heated to reflux for 48 h. After evaporation of the dioxane, deionized water (100 mL) was added, and the aq. layer was extracted with chloroform (3 100 mL). The combined organic extract was washed with brine (100 mL), dried with magnesium sulfate, and filtered. Activated charcoal was added, and the mixture was heated and filtered while hot. After reduction of the volume, the crude product was recrystallized from chloroform/petrolether, yielding 1.14 g (1.29mmol, 88%) of a colorless solid. M. p.: >300 C. 1H NMR (600MHz, CDCl3): delta=8.88 (mc(d), 6H, J = 8.1 Hz, Ar-H-3, 5), 8.69 (s, 3H, Ar-H-4'), 8.56 (s, 6H, Ar-H-2', 6'), 7.87 (mc(d), 6H, J = 8.1Hz, Ar-H-2, 6), 4.01 (s, 18 H, CO2CH3) ppm. 13C NMR (150MHz, CDCl3): delta= 171.2 (s, tri-C-2, 4, 6), 166.1 (s, CO2Me), 142.9 (s, Ar-C-1), 141.1 (s, Ar-C-1'), 136.0 (s, Ar-C-4), 132.4 (d, Ar-C-2', 6'), 131.3 (s, Ar-C-3', 5'), 129.9(d, Ar-C-4'), 129.7 (d, Ar-C-3, 5), 127.4 (d, Ar-C-2, 6), 52.6 (q, CO2CH3) ppm. MS (MALDI, Cl-CCA): m/z =886 [M+ H]+. IR (ATR): = 3005 (aryl-H), 2993 (C-H-val.), 1690 (C=O), 1609, 1581, 1509 (arom. C=C, arom.C=N), 1435 (CH-def.), 1349 (C-N-val.), 813 (1, 4-disubst. aryl, 1, 3, 5-trisubst. aryl) cm1. Elemental analysis(C51H39N3O12) (885.87): calcd. C 69.15 H 4.44 N 4.74; (C51H39N3O12 0.1 CHCl3) (897.81): calcd. C 68.36 H4.39 N 4.68; found C 68.26 H 4.28 N 4.81.Under nitrogen, a solution of 2, 4, 6-tris(4-bromophenyl)-1, 3, 5-triazine (3a, 803 mg, 1.47 mmol) [20], dimethyl 5-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-isophthalate (4, 1.69 g, 5.28 mmol), potassium acetate (1.30 g, 13.2 mmol), and 1, 1'-bis(diphenylphosphine)ferrocene-palladium(II) chloride (120 mg, 164 mol) in a 10:1 mixture (90 mL) of 1, 4-dioxane and water was heated to reflux for 48 h. After evaporation of the dioxane, deionized water (100 mL) was added, and the aq. layer was extracted with chloroform (3 100 mL). The combined organic extract was washed with brine (100 mL), dried with magnesium sulfate, and filtered. Activated charcoal was added, and the mixture was heated and filtered while hot. After reduction of the volume, the crude product was recrystallized from chloroform/petrolether, yielding 1.14 g (1.29mmol, 88%) of a colorless solid. M. p.: >300 C. 1H NMR (600MHz, CDCl3): delta=8.88 (mc(d), 6H, J = 8.1 Hz, Ar-H-3, 5), 8.69 (s, 3H, Ar-H-4'), 8.56 (s, 6H, Ar-H-2', 6'), 7.87 (mc(d), 6H, J = 8.1Hz, Ar-H-2, 6), 4.01 (s, 18 H, CO2CH3) ppm. 13C NMR (150MHz, CDCl3): delta= 171.2 (s, tri-C-2, 4, 6), 166.1 (s, CO2Me), 142.9 (s, Ar-C-1), 141.1 (s, Ar-C-1'), 136.0 (s, Ar-C-4), 132.4 (d, Ar-C-2', 6'), 131.3 (s, Ar-C-3', 5'), 129.9(d, Ar-C-4'), 129.7 (d, Ar-C-3, 5), 127.4 (d, Ar-C-2, 6), 52.6 (q, CO2CH3) ppm. MS (MALDI, Cl-CCA): m/z =886 [M+ H]+. IR (ATR): = 3005 (aryl-H), 2993 (C-H-val.), 1690 (C=O), 1609, 1581, 1509 (arom. C=C, arom.C=N), 1435 (CH-def.), 1349 (C-N-val.), 813 (1, 4-disubst. aryl, 1, 3, 5-trisubst. aryl) cm1. Elemental analysis(C51H39N3O12) (885.87): calcd. C 69.15 H 4.44 N 4.74; (C51H39N3O12 0.1 CHCl3) (897.81): calcd. C 68.36 H4.39 N 4.68; found C 68.26 H 4.28 N 4.81.Under nitrogen, a mixture of 2-(4-bromo-3-nitrophenyl)-4, 6-bis(4-bromophenyl)-1, 3, 5-triazine(3b, 100 mg, 170 mumol) [13], dimethyl 5-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-isophthalate(4, 245 mg, 765 mumol), tetrakis(triphenylphosphine)-palladium(0) (30 mg, 26 mumol), and potassium phosphate (234 mg, 1.10 mmol) in a mixture of 1, 4-dioxane (10 mL) and deionized water (1 mL) was heated to reflux for 48 h. After evaporation of the dioxane in vacuo, the residue was dissolved in water (25 mL) and extracted with chloroform (3 x 25 mL). The combined organic layer was washed with brine (25 mL), dried with magnesium sulfate, and filtered. Activated charcoal was added to the filtrate, and the mixture was heated and filtered through celite while hot. The solvent was evaporated in vacuo and the residue was recrystallized from a hot mixture of toluene and n-heptane yielding131 mg (141 mumol, 83%) of a colorless solid, m. p.: >300 C. 1H NMR (500 MHz, CDCl3): = 9.33(s, 1 H, Ar-H-3), 9.02 (d, 1 H, J = 7.0 Hz, Ar-H-5), 8.86 (d, 4 H, J = 8.0 Hz, Ar'-H-3, 5), 8.75 (s, 1 H, Ar-H-4'), 8.69 (s, 2 H, Ar-H-2', 6'), 8.53 (s, 4 H, Ar'-H-2', 6'), 8.23 (s, 2 H, Ar'-H-4'), 7.87 (d, 4 H, J = 8.0Hz, Ar'-H-2, 6), 7.65 (d, 1 H, J = 7.0 Hz, Ar-H-6), 4.01 (s, 12 H, Ar'-CO2CH3), 3.98 (s, 6 H, Ar-CO2CH3)ppm. 13C NMR (125 MHz, CDCl3): delta= 171.6 (s, tri-C-4, 6), 169.3 (s, tri-C-2), 166.0 (s, Ar-CO2Me), 166.0(s, Ar'-CO2Me), 149.1 (s, Ar-C-2), 143.3 (s, Ar'-C-1), 140.8 (s, Ar'-C-1'), 138.0 (s, Ar-C-1), 137.2 (Ar-C-1'), 135.2 (s, Ar'-C-4), 133.1 (d, Ar'-C-4'), 132.5 (d, Ar-C-5), 132.4 (d, Ar'-C-2', 6'), 132.4 (d, Ar-C-6), 131.4(s, Ar'-C-3', 5'), 131.3 (s, Ar-C-3', 5'), 130.6 (d, Ar-C-4'), 130.0 (s, Ar-C-4), 129.9 (d, Ar-C-2', 6'), 129.7(d, Ar'-C-3, 5), 127.5 (d, Ar'-C-2, 6), 124.8 (d, Ar-C-3), 52.6 (q, Ar-CO2CH3), 52.6 (q, Ar'-CO2CH3) ppm.MS (MALDI, Cl-CCA): m/z = 931 [M + H]+. IR (ATR):e= 3005 (aryl-H), 2992, 2952 (C-H-val.), 1719(C=O), 1607, 1575, 1506 (arom. C=C, arom. C=N), 1515 (NO2), 1431 (CH-def.), 1341 (C-N-val.), 817(1, 4-disubst. aryl, 1, 3, 4-trisubst. aryl) cm1. Elemental analysis (C51H38N4O14) (930.87): calcd. C 65.80H 4.11 N 6.02; found C 65.50 H 4.12 N 5.91.Under nitrogen, 2-(4-bromo-3-methoxyphenyl)-4, 6-bis(4-bromophenyl)-1, 3, 5-triazine (3c, 100 mg, 175 mumol) [13], dimethyl 5-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl)-isophthalate (4, 252 mg, 788 mumol) and potassium phosphate (234 mg, 1.10 mmol) were mixed with a mixture of 1, 4-dioxane(10 mL), and deionized water (1 mL). Tetrakis(triphenylphosphine)-palladium(0) (30 mg, 26 mumol)was added, and the mixture was stirred for 48 h at 100 C. After evaporation of the dioxane in vacuo, chloroform (25 mL) was added to the residue, and the resulting mixture was washed with deionized water (3 25 mL). The organic layer was dried with magnesium sulfate, filtered, and heated with little activated charcoal. After filtration through celite while hot, the solvent was evaporated in vacuo until the residue turned turbide. Recrystallization from a boiling mixture of chloroform and petrol ether (b.p. 40-60 C) yielded 130 mg (142 mumol, 81 %) of a colorless solid, m. p.: >300 C. 1H NMR (500 MHz, CDCl3): delta= 8.88 (d, 4 H, J = 8.5 Hz, Ar'-H-3, 5), 8.70 (t, 2 H, J = 1.5 Hz, Ar'-H-4'), 8.67 (t, 1 H, J = 1.6 Hz, Ar-H-4'), 8.55 (d, 4 H, J = 1.5 Hz, Ar'-H-2', 6'), 8.49 (dd, 1 H, J = 7.9 Hz, J = 1.4 Hz, Ar-H-5), 8.47 (d, 2 H, J = 1.6 Hz, Ar-H-2', 6'), 8.42 (d, 1 H, J = 1.4 Hz, Ar-H-3), 7.88 (d, 4 H, J = 8.5 Hz, Ar'-H-2, 6), 7.56 (d, 1 H, J = 7.9 Hz, Ar-H-6), 4.07 (s, 3 H, Ar-OCH3), 4.01 (s, 12 H, Ar'-CO2CH3), 3.99 (s, 6 H, Ar-CO2CH3) ppm.13C NMR (125 MHz, CDCl3): = 171.2 (s, tri-C-4, 6), 171.1 (s, tri-C-2), 166.3 (s, Ar-CO2Me), 166.1 (s, Ar'-CO2Me), 156.7 (s, Ar-C-2), 143.0 (s, Ar'-C-1), 141.0 (s, Ar'-C-1'), 138.7 (s, Ar-C-1'), 137.4 (s, Ar-C-4), 135.9 (s, Ar'-C-4), 134.9 (d, Ar-C-2', 6'), 132.7 (s, Ar-C-1), 132.3 (d, Ar'-C-2', 6'), 131.4 (s, Ar-C-3', 5').131.0 (d, Ar-C-6), 130.5 (s, Ar'-C-3', 5'), 129.9 (d, Ar'-C-4'), 129.7 (d, Ar'-C-3, 5), 129.6 (d, Ar-C-4'), 127.4(d, Ar'-C-2, 6), 121.9 (d, Ar-C-5), 111.2 (d, Ar-C-3), 55.9 (q, Ar-OCH3), 52.5 (q, Ar'-CO2CH3), 52.4 (q, Ar-CO2CH3) ppm. MS (MALDI, Cl-CCA): m/z = 916 [M + H]+. IR (ATR):e~ = 3005 (aryl-H), 2954(C-H-val.), 1728 (C=O), 1606, 1578, 1517 (arom. C=C, arom. C=N), 1429 (CH-def.), 1371 (OCH3), 1342(C-N-val.), 809 (1, 4-disubst. aryl, 1, 3, 4-trisubst. aryl) cm1. Elemental analysis (C52H41N3O13) (915.89):calcd. C 68.19 H 4.51 N 4.59; (C52H41N3O130.2 CHCl3) (939.71): calcd. C 66.71 H 4.42 N 4.47; found C66.34 H 4.74 N 4.86.

Molecular Weight:320.1
Hydrogen Bond Acceptor Count:6
Rotatable Bond Count:5
Exact Mass:320.1431186
Monoisotopic Mass:320.1431186
Topological Polar Surface Area:71.1
Heavy Atom Count:23
Complexity:435
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes