Supplementary Data Synthesis, Chemo-selective Properties of Substituted 9-Aryl-9H-fluorenes from Triarylcarbinols and Enantiomerical Kinetics of Chiral 9-Methoxy-11-(naphthalen-1-yl)-11H-benzo[a]fluorene Ming-yu Teng* a,b, Ying Liu b, Shao-lu Li b, Guoli Huang a,b, Juli Jiang* b, and Leyong Wang* b a Facult of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, P. R. China; E-mail: mingyu_teng@hotmail.com b Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China; E-mail: jjl@nju.edu.cn; lywang@nju.edu.cn Contents I. General Procedure for Preparation of 1c, 1d, 1e, 1g, 1j, 1k... S2 II. General Procedure for Preparation of 1i... S5 III. NMR Spectral Characterization ( 1 H and 13 C NMR for 1c, 1d, 1e, 1g, 1i, 1j, 1k, 2a, 2b, 2c, 2d, 2e, 2f, and 2g)... S7 IV. Variable-temperature 1 H NMR and Eyring Plot Analysis of 2g and 2g... S21 V. EI-TF HRMS Spectra of 1d, 1e, 2a, and 2g... S23 VI. HPLC of 2g.... S25 VII. HMBC/HMQC 2D NMR Spectroscopy of 2g..... S26 Reference..... S29 S1
I. General Procedure for Preparation of 1c, 1d, 1e, 1g, 1h, 1k, 1l) (except 1i). [S1] R 3 R 1 Br Mg THF R 1 MgBr + R 3 CEt 1. THF H 2. H + R 1 R 2. R 1 = R 2 A mixture of bromoarene (32.0 mmol) and 20 ml of anhydrous THF is added to magnesium (2.30 g, 96.0 mmol), and the flask warmed gently until the reaction start. A mixture of bromoarene (64.0 mmol) and 40 ml of anhydrous THF is run in at such a rate as to cause vigorous refluxing, the mixture is warmed to refluxing for two hours, in order to dissolve all the magnesium. The reaction was cooled to room temperature, aromatic ester (40.0 mmol) is added into the Grinard solution, and the mixture is warmed to reflux over night. The reaction mixture is cooled in an ice-salt bath and then added slowly, with constant stirring, into 60 ml saturated NH 4 Cl aqueous solution. The mixture is distilled to remove THF and stream-distilled to remove biphenyl and unchanged bromobenzene. The product is filtered, washed with water, and recrystallized from ethanol and water. (4-Bromophenyl)bis(3-methoxyphenyl)methanol (1c) 5' 6' 2 3 3' 4' 2' H 6 5 Br Colorless solid; m.p. 127-128 ºC; R f = 0.43 (petroleum ether/ethyl acetate = 4/1); product 1.41 g (yield 35.3%). 1 H NMR (300M Hz, CDCl 3, TMS): δ = 7.42 (d, 2H, J = 8.7 Hz; H-3, 5), 7.23 (t, 2H, J = 8.7 Hz; H-5 ), 7.18 (d, 2H, J = 8.7 Hz; H-2, 6), 6.84 (s, 2H; H-2 ), 6.84-6.78 (m, 4H; H-4, 6 ), 3.75 (s, 6H; H-3 ). 13 C NMR (75M Hz): δ = 159.2, 147.8, 145.5, 130.1, 129.6, 129.0, 121.4, 120.3, 113.8, 112.5, 81.5, 55.1. FT-IR (cm -1 ): ν max (KBr/cm -1 ), 3554, 2969, 1597, 1484, 1421, 1321, 1286, 1251, 1166, 1137, 1072, 1042, 1022, 1010, 934, 865, 833, 775, 704. Anal. Calc. for C 21 H 19 Br 3 : C, 63.17; H, 4.80. Found: C, 63.13; H, 4.69. (2,5-Dichlorophenyl)bis(3-methoxyphenyl)methanol (1d) 5' 6' 6 Cl 3' 4' 2' H Cl 3 4 S2
Colorless solid; m.p. 42-44 ºC; R f = 0.53 (petroleum ether/ethyl acetate = 4/1); product 6.59 g (yield 42.3%). 1 H NMR (300M Hz, CDCl 3, TMS): δ = 7.32 (d, 1H, J = 8.4 Hz; H-3), 7.24 (t, 2H, J = 8.4 Hz; H-5 ), 7.23 (dd, 1H, J = 8.4, 2.1 Hz; H-4), 6.89 (t, 2H, J = 2.1 Hz; H-2 ), 6.85 (dd, 2H, J = 8. 4, 2.1 Hz; H-4 ), 6.76 (d, 2H, J = 8.4 Hz; H-6 ), 6.74 (d, 2H, J = 2.1 Hz, H-6), 3.78 (s, 6H; H-3 ). 13 C NMR (75M Hz): δ = 159.4, 146.2, 145.3, 132.5, 132.2, 131.4, 131.3, 129.0, 120.1, 113.4, 112.8, 82.1, 55.1. FT-IR (cm -1 ): max (KBr/cm -1 ), 3445, 2956, 1599, 1559, 1487, 1457, 1289, 1250, 1105, 1047, 776, 758, 699, 553. HRMS (EI): m/z calcd for C 21 H 18 Cl 2 3 [M + ]: 388.0633; found: 388.0659. Bis(3-methoxyphenyl)(naphthalen-1-yl)methanol (1e) 5' 6' 2 3 3' 4' 2' H 8 7 6 4 5 Colorless solid; m.p. 71-73 ºC; R f = 0.42 (petroleum ether/ethyl acetate = 4/1); product 6.04 g (yield 62.7%). 1 H NMR (300M Hz, CDCl 3, TMS): δ = 8.11 (d, 1H, J = 8.7 Hz; H-8), 7.85-7.78 (m, 2H; H-4, 5), 7.39 (td, 1H, J = 8.8, 0.9 Hz; H-6), 7.31-7.27 (m, 1H; naphthalen H), 7.22 (t, 2H, J = 8.1 Hz; H-5 ) 7.17-7.12 (m, 1H; naphthalen H), 6.95 (t, 2H, J = 2.1 Hz; H-2 ), 6.88 (dd, 2H, J = 7.5, 0.9 Hz; naphthalen H), 6.84-6.81 (m, 3H; H-6, naphthalen 2-H), 3.74 (s, 6H; H-3 ). 13 C NMR (75M Hz): δ = 159.3, 148.4, 141.7, 134.8, 131.1, 129.3, 128.9, 128.1, 127.8, 125.6, 125.2, 124.2, 120.3, 113.6, 113.5, 112.3, 83.1, 55.1. FT-IR (cm -1 ): ν max (KBr/cm -1 ), 3454, 2935, 1597, 1486, 1463, 1432, 1316, 1289, 1250, 1143, 1040, 865, 781, 760, 700. HRMS (EI): m/z calcd for C 25 H 22 3 [M] + : 370.1569; found: 370.1575. (3-Methoxyphenyl)dinaphthalen-1-ylmethanol (1g) 4 5 3 2 H 8 6' 2' 5' 4' 3' 6 7 Colorless solid; m.p. = 206-207 ºC; R f = 0.63 (petroleum ether/ethyl acetate = 4/1); product 4.06 g (yield 52.1%).. S3
1 H NMR (300M Hz, CDCl 3, TMS): δ = 8.26 (brs), 2H; H-8), 7.87 (d, 2H, J = 8.1 Hz; H-5), 7.80 (d, 2H, J = 8.1 Hz; H-4), 7.41 (td, 2H, J = 7.5, 0.9 Hz; H-6), 7.28 (t, 2H, J = 7.5 Hz; H-7), 7.23-7.18 (m, 3H, H-3, 5 ), 7.05 (s, 1H; H-2 ), 6.88-6.82 (m, 4H, H-2, 4 6 ), 3.75 (s, 6H; H-3 ). 13 C NMR (75M Hz): 159.4, 148.6, 141.9, 135.0, 131.2, 129.4, 129.2, 128.9, 128.8, 128.4, 128.2, 125.5, 124.3, 120.5, 113.9, 112.1, 85.1, 55.1. FT-IR (cm -1 ): ν max (KBr/cm -1 ), 3412, 3043, 1582, 1504, 1482, 1434, 1393, 1284, 1237, 1160, 1019, 875, 833, 806, 793, 776, 698, 560. Anal. Calc. for C 28 H 22 2 : C, 86.13; H, 5.68. Found: C, 86.21; H, 5.47. phenylbis(3-(trifluoromethyl)phenyl)methanol (1j) F 3 C 5' 6' 2 3 4' F 3 C 2' H 6 5 4 Colorless oil; R f = 0.30 (petroleum ether/ethyl acetate = 10/1); product 1.68 g (yield 42.4%). 1 H NMR (300M Hz, CDCl 3, TMS): δ = 7.68 (s, 2H, H-2 ), 7.57 (d, 2H; J = 6.3 Hz; H-4 ), 7.48-7.43 (m, 4H; H-5, 6 ), 7.36 (m, 1H; H-4), 7.34 (d, 2H, J = 2.4 Hz; H-2, 6) 7.22-7.18 (m, 2H; H-3, 5), 2.91 (s, 1H; -H). 13 C NMR (75M Hz): δ = 146.1, 144.5, 130.3, 129.4 (t, J = 31.9), 127.5, 127.5, 127.1, 126.7, 124.9, 123.4, 123.3, 121.3, 80.6. FT-IR (cm -1 ): ν max (KBr/cm -1 ), 3454, 3076, 2926, 1492, 1446, 1330, 1168, 1120, 1076, 806, 703, 675. Anal. Calc. for C 21 H 14 F 6 : C, 63.64; H, 3.56. Found: C, 63.69; H, 3.47. (3-methoxyphenyl)bis(3-(trifluoromethyl)phenyl)methanol (1k) 5' F 3 C 6' 2 3 Me 4' F 3 C 2' H 6 5 4 Colorless solid; m.p. = 73-74 ºC; R f = 0.43 (petroleum ether/ethyl acetate = 10/1); product 1.59 g (yield 37.3%). 1 H NMR (300M Hz, CDCl 3, TMS): δ = 7.68 (s, 2H, H-2 ), 7.57 (d, 2H; J = 6.3 Hz; H-4 ), 7.47-7.41 (m, 4H; H-5, 6 ), 7.27 (t, 1H; J = 8.1 Hz; H-5), 6.87 (dd, 1H, J = 8.1, 2.1 Hz; H-4), 6.78 (t, 1H; J = 2.1 Hz; H-2), 6.75 (d, 1H; J = 7.5 Hz; H-6), 3.75 (s, 3H; -Me), 2.92 (s, 1H; -H). S4
13 C NMR (75M Hz): δ = 159.6, 147.2, 147.0, 131.3, 130.4 (t, J = 31.7), 129.6, 128.8, 128.6, 124.5, 124.3 120.1, 114.0, 113.1, 81.4, 55.2. FT-IR (cm -1 ): ν max (KBr/cm -1 ), 3507, 2955, 1597, 1489, 1470, 1437, 1330, 1255, 1164, 1123, 1076, 1034, 809, 771, 705. Anal. Calc. for C 22 H 16 F 6 2 : C, 61.98; H, 3.78. Found: C, 61.93; H, 3.87. II. Procedure for Preparation of 1i A mixture of 1-bromo-3-(trifluoromethyl)benzene (4.95, 22.0 mmol) and 40 ml of anhydrous THF is added one third to magnesium (0.53g, 22.0 mmol), and the flask warmed gently until the reaction start. The residual mixture of benzophenone and anhydrous THF is run in at such a rate as to cause vigorous refluxing, the mixture is warmed to refluxing for two hours, in order to dissolved all the magnesium. The reaction was cooled to room temperature, 20.0 mmol of benzophenone is added into the Grinard solution, the mixture is warmed to reflux over night. The reaction mixture is cooled in an ice-salt bath and then added slowly, with constant stirring, into 16 ml saturated NH 4 Cl aqueous solution. The mixture is distilled to remove THF and stream-distilled to remove biphenyl and unchanged bromobenzene. The crude product was purified by column chromatography with silica gel using CH 2 Cl 2 as eluant to afford pure product. diphenyl(3-(trifluoromethyl)phenyl)methanol (1i) Colorless oil; R f = 0.41 (petroleum ether/ethyl acetate = 10/1); product 2.71g (yield 41.3 %). 1 H NMR (300M Hz, CDCl 3, TMS): δ = 7.75 (s, 1H, H-2 ), 7.58 (d, 1H; J = 7.8 Hz; H-4 ), 7.51-7.44 (m, 2H; H-5, 6 ), 7.39-7.27 (m, 10H; H-2, 3, 4, 5, 6), 2.98 (s, 1H; -H). 13 C NMR (75M Hz): δ = 147.9, 146.3, 131.5, 128.9, 128.8, 128.3, 127.9, 127.7, 124.5, 124.5, 124.2, 124.1, 81.9. FT-IR (cm -1 ): ν max (KBr/cm -1 ), 3449, 2925, 2855, 1448, 1167, 1128, 1076, 1018, 804, 755, 702, 661. Anal. Calc. for C 20 H 15 F 3 : C, 73.16; H, 4.60. Found: C, 73.07; H, 4.71. References [S1] Bachmann, W. E., Hetzner, H. P. rg. Synth. 1955, Coll. Vol. 3, 839. S5
III. NMR Spectral Characterization ( 1 H and 13 C NMR for 1c, 1d, 1e, 1g, 1i, 1j, 1k, 2a, 2b, 2c, 2d, 2e, 2f, 2g, and 3a) 1c in CDCl 3 7.427 7.399 7.248 7.242 7.214 7.187 7.180 7.157 6.839 6.828 6.801 6.775 6.772 3.737-0.011 Br Me Me 2.86 2.91 3.53 2.00 7.50 7.40 7.30 7.20 7.10 7.00 6.90 6.80 6.70 water 6.02 2.91 2.86 3.53 2.00 10.0 5.0 0.0 159.226 147.757 145.504 130.891 129.577 128.972 121.357 120.265 113.826 112.482 81.502 77.375 76.952 76.528 55.136 H Br 150 100 50 0 S6
1d in CDCl 3 7.325 7.297 7.266 7.258 7.244 7.239 7.213 7.208 6.892 6.885 6.879 6.867 6.861 6.840 6.834 6.778 6.752 6.746 6.737 3.767-0.000000 Cl Cl H 7.40 7.30 7.20 7.10 7.00 6.90 6.80 6.70 EtH EtH 6.00 3.01 1.03 2.98 1.01 3.42 10.0 5.0 0.0 159.419 146.153 145.252 132.481 132.225 131.393 131.316 128.990 120.301 120.113 113.420 112.818 82.118 55.123 Cl H Cl 150 100 50 0 S7
1e in CDCl 3 159.327 148.408 141.710 134.829 131.147 129.560 129.315 129.213 128.866 128.107 127.844 125.557 125.227 124.206 120.335 113.609 113.521 112.264 83.103 77.377 76.953 76.529 55.140 55.046 H 200 150 100 50 0 S8
1g in CDCl 3 159.421 148.580 141.874 134.994 131.232 129.437 129.159 128.877 128.763 128.449 128.235 125.475 125.241 124.262 120.505 113.852 112.128 85.110 77.391 77.173 76.968 76.545 55.069 H 200 150 100 50 0 S9
1i in CDCl 3 146.197 131.439 128.759 128.218 127.829 127.697 124.428 124.382 124.124 124.073 77.445 77.021 76.599 29.715 H F 3 C 200 150 100 50 0 S10
1j in CDCl 3 0.00000 2.905 7.184 7.191 7.202 7.206 7.216 7.251 7.340 7.346 7.357 7.364 7.429 7.437 7.449 7.475 7.561 7.577 7.582 7.678 F 3 C H 2.02 2.08 4.27 3.08 2.05 CF 3 7.70 7.60 7.50 7.40 7.30 7.20 7.10 water petroleum 2.02 2.08 4.27 3.08 2.05 1.00 10.0 5.0 0.0 29.796 76.626 77.054 77.476 81.688 122.378 123.764 124.441 124.533 125.989 126.935 127.842 128.231 128.581 128.655 130.533 130.966 131.429 145.636 147.191 F 3 C H CF 3 200 150 100 50 0 S11
1k in CDCl 3 55.23 76.58 77.01 77.43 81.43 113.12 114.01 120.22 124.33 124.53 128.57 128.75 129.55 131.31 146.96 147.16 159.63 F 3 C H CF 3 200 150 100 50 0 S12
2a in CDCl 3 7.592 7.564 7.254 7.228 7.202 7.175 6.911 6.904 6.884 6.876 6.834 6.828 6.791 6.785 6.764 6.758 6.715 6.689 6.641 6.635 4.919 3.770 3.735 0.000000 7.50 7.00 3.09 5.86 1.00 2.01 1.96 1.07 1.03 1.01 1.05 1.98 10.0 5.0 0.0 159.978 158.993 149.120 143.401 134.130 129.817 120.987 119.820 114.430 113.516 112.047 111.024 77.584 77.160 76.736 55.642 55.284 54.623 200 150 100 50 0 S13
2b in CDCl 3 0,02 3,78 3,79 4,02 4,96 6,83 6,83 6,89 6,90 6,92 6,93 7,09 7,10 7,12 7,13 7,26 7,26 7,27 7,29 7,59 7,61 Me Me 7.50 7.00 2.09 3.98 2.42 2.45 2.16 1.00 6.08 10.0 5.0 0.0 158.885 149.261 141.771 134.022 128.786 128.729 128.425 127.202 126.888 126.838 124.392 119.749 117.540 113.363 113.115 110.953 110.527 109.249 55.523 54.552 Me Me 200 150 100 50 0 S14
2c in CDCl 3 S15
2d in CDCl 3 7.611 7.584 7.453 7.424 7.258 7.151 7.143 7.122 7.114 6.944 6.936 6.916 6.909 6.873 6.502 6.493 5.614 3.794 1.518-0.00000 Cl Cl 7.50 7.00 6.50 6.66 1.00 1.01 2.10 2.29 1.13 1.05 2.20 10.0 5.0 0.0 159.052 147.850 141.949 134.185 133.193 132.798 130.724 129.067 128.416 120.090 113.733 110.968 55.651 50.227 Cl Cl 200 150 100 50 0 S16
2e in CDCl 3 160.041 159.596 150.960 143.462 141.676 139.452 134.102 133.016 130.597 130.013 129.043 128.962 126.455 124.859 124.453 120.619 120.387 118.306 114.203 113.052 111.832 111.073 77.583 77.160 76.737 55.635 55.213 54.154 200 150 100 50 0 S17
2f in CDCl 3 144.882 141.813 139.337 133.485 130.367 129.206 129.060 128.947 128.875 126.810 126.605 125.195 123.950 118.541 77.584 77.160 76.737 54.246 200 150 100 50 0 S18
2g in CDCl 3 159.124 151.032 142.032 139.688 137.685 134.342 133.814 132.900 132.145 130.057 129.225 128.856 128.783 128.713 128.557 128.384 128.243 127.124 126.396 126.233 126.084 125.674 125.593 125.397 124.681 124.380 124.289 123.548 120.390 118.431 118.182 113.224 112.407 110.801 110.109 55.328 48.037 200 150 100 50 0 S19
2g in DMS-d6 8.9826 8.9537 8.1739 8.1423 8.1143 8.0570 8.0299 7.9961 7.9698 7.9474 7.9198 7.9081 7.8229 7.8188 7.7948 7.7677 7.7134 7.6887 7.3544 7.2062 7.1940 7.1814 7.1390 7.1138 6.9895 6.9821 6.9617 6.9543 6.6859 6.6797 6.6650 6.4441 6.3776 6.3546 5.8528 3.6488 3.6066 3.3507 2.5078 2.5023 2.4968 Me 0.65 0.40 0.39 0.40 0.95 0.45 1.78 0.36 0.99 0.86 1.90 0.66 0.40 0.75 1.96 0.32 1.42 0.44 0.69 1.01 0.41 0.63 0.62 0.40 DMS 8.00 7.50 7.00 6.50 water 3.00 0.12 0.35 0.63 0.62 0.40 1.01 0.41 0.66 0.75 0.40 1.96 0.44 1.42 0.32 0.69 0.40 0.95 0.45 1.78 0.40 0.65 1.90 0.86 0.99 0.36 0.39 0.63 10.0 2g in benzene-d6 5.0 0.0 S20
IV. Variable-temperature 1 H NMR and Eyring Plot Analysis of 2g and 2g (300 MHz, DMS) 393 K 388 K 383 K 378 K 373 K 363 K 338 K 297 K 9.0 8.0 7.0 6.0 5.0 4.0 3.0 S21
ln(k)\ln(k/t) Electronic Supplementary Material (ESI) for RSC Advances T (K) rate constant k/s -1 1/T (K -1 ) 1/T 1000 ln(k) ln(k/t) ΔG (J/mol) 3.630E+02 4.000E+00 2.7548E-03 2.7548209 1.3863-4.50811 8.5313E+04 3.730E+02 8.000E+00 2.6810E-03 2.6809651 2.0794-3.84214 8.5598E+04 3.780E+02 1.200E+01 2.6455E-03 2.6455026 2.4849-3.44999 8.5513E+04 3.830E+02 2.000E+01 2.6110E-03 2.6109661 2.9957-2.9523 8.5059E+04 3.880E+02 3.500E+01 2.5773E-03 2.5773196 3.5553-2.40566 8.4406E+04 3.930E+02 5.000E+01 2.5445E-03 2.5445293 3.9120-2.06179 8.4370E+04 1/T - ln(k)\ln(k/t) 5.0000 4.0000 3.0000 2.0000 1.0000 0.0000-1.00002.5000-2.0000 E-03-3.0000-4.0000-5.0000-6.0000 2.5500 E-03 2.6000 E-03 2.6500 E-03 1/T ln(k) = -12364*1/T + 35.323 2.7000 E-03 2.7500 E-03 R 2 = 0.9875 2.8000 E-03 ln(k) ln(k/t) = -11986*1/T + 28.389 R 2 = 0.9868 ln(k/t) R 8.314E+0 ln(k)=lna-ea/rt Ea/R 12364 Ea (J/mol) 102.794E+3 -ΔH / R -1.199E+04 ln(k/t) = 23.76 + ΔS /8.31- ΔH /(8.31T) ΔH (J/mol) 99651.60 ΔG =(23.76-ln(k/T))*R*T ΔG =at(10.319-log(k/t)) a=1.914*0.01 (ΔG in kj/mol) a=1.914*10 (ΔG in J/mol) ΔG =ΔH -TΔS ΔS (J/mol*K) 37.6783112 (T = 373K) S22
V. MS Spectra 1d 1e S23
2a 2g S24
VI. HPLC of 2g. S25
VII. H-HCSY/HMBC/HMQC 2D NMR Spectroscopy of 2g (500M Hz, in CDCl 3 ). S26
S27
S28
Reference [S1]. Bachmann, W. E.; Hetzner H. P. rg. Synth. 1955, Coll. Vol. 3, 839-840. S29