Supporting information Spectroscopic data of compounds 1a-f Benzyl bromide (1a) Yield: 81%. Colorless oil. b.p. 79-82 o C/15 mmhg (Lit. 83.5 84 o C/13 mmhg). 1 1 H NMR (CDCl 3 ): δ 4.45 (2H, s, PhCH 2 Br), 7.35-7.48 (5H, m, CH). 13 C NMR (CDCl 3 ): δ 33.7 (PhCH 2 Br), 128.4 (CH-4), 128.8 (CH-3,5), 129.1 (CH-2,6), 137.8 (C-1). IR (Nujol): 2954 (vs), 2924 (vs), 2854 (vs), 1462 (s), 1377 (s) cm -1. o-bis(bromomethyl)benzene (1b) Yield: 75%. White solid. m.p.: 98.4-99.8 C (Lit. 98-99 o C). 2 1 H NMR (CDCl 3 ): δ 4.68 (4H, s, PhCH 2 Br), 7.26-7.39 (4H, m, CH). 13 C NMR (CDCl 3 ): δ 30.1 (PhCH 2 Br), 129.6 (CH-4,5), 131.2 (CH-3.6), 136.7 (C-1,2). IR (KBr): 1437 (w), 1419 (w), 1227 (s), 1198 (s), 848 (w), 750 (w) cm -1. m-bis(bromomethyl)benzene (1c) Yield: 58%. White solid. m.p.: 77.7-79.4 C (Lit. 75-76 o C). 3 1 H NMR (CDCl 3 ): δ 4.48 (4H, s, PhCH 2 Br), 7.33 (3H, m, PhCH), 7.43 (1H, m, PhCH). 13 C NMR (CDCl 3 ): δ 33.0 (PhCH 2 Br), 129.1 (CH-4,6), 129.3 (CH-5), 129.6 (CH-2), 138.4 (C-1,3). IR (KBr): 1486 (w), 1436 (vs), 1210 (vs), 1163 (s), 898 (w), 798 (s) cm -1. p-bis(bromomethyl)benzene (1d) Yield: 15%. White solid. m.p.: 143.6-145.8 C (Lit. 142-144 o C). 2 1 H NMR (CDCl 3 ): δ 4.48 (4H, s, PhCH 2 Br), 7.37 (4H, s, CH). 13 C NMR (CDCl 3 ): δ 33.0 (PhCH 2 Br), 129.6 (CH-2,3,5,6), 138.1 (C-1,4). IR (KBr): 2346 (s), 1456 (w), 1433 (w), 1221 (s), 1211 (s), 1187 (s), 766 (s), 738 (s) cm -1. 1,3,5-tris(Bromomethyl)benzene (1e) Yield: 42%. White solid. m.p.: 104.9-107.5 C (Lit. 101-105). 4 1 H NMR (CDCl 3 ): δ 4.45 (6H, s, PhCH 2 Br), 7.26-7.36 (3H, s, CH). 13 C NMR (CDCl 3 ): δ 32.4 (PhCH 2 Br), 139.2 (CH-2, 4, 6), 129.8 (C-1,3,5). IR (KBr): 1256 (vs), 1152 (s), 1026 (s), 973 (s), 727 (s) cm -1. 1-Bromo-2,4,6-tris(bromomethyl)benzene (1f) Yield: 38%. White solid. m.p.: 100.1-103.3 C (Lit. 98-100). 5 1 H NMR (CDCl 3 ): δ 4.41 (2H, s, Ph-4-CH 2 Br), 4.61 (4H, s, Ph-2,6-CH 2 Br), 7.44 (2H, s, CH). 13 C NMR (CDCl 3 ): δ 31.3 (Ph-2,6-CH 2 Br), 33.4 (Ph-4-CH 2 Br), 126.5 (C-1), 131.8 (CH-3,5), 138.0 (C-2,6), 139.0 (C-4). IR (KBr): 3441 (vs), 1212 (s), 703 (s) cm -1.
NMR spectra of compounds 2a-g Perfluoro-tert-butoxymethylbenzene (2a) 5.04 2.00 7.44 7.40 7.39 7.37 5.06 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 1 H NMR spectrum of 2a 81.4 81.1 80.8 80.5 80.2 79.9 72.3 54.5 54.3 54.0 53.7 53.5 129.5 129.3 128.6 125.5 122.6 119.7 116.8 135.5 140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 13 C NMR spectrum of 2a
-164.90-72.64-45 -55-65 -75-85 -95-105 -115-125 -135-145 -155-165 -175 19 F NMR spectrum of 2a
o-bis(perfluoro-tert-butoxymethyl)benzene (2b) 3.96 4.00 5.15 7.45 8.5 8.0 7.5 7.0 6.5 6.0 f1 5.5 5.0 4.5 4.0 1 H NMR spectrum of 2b 125.4 122.4 119.5 116.6 80.9 80.6 80.3 80.0 79.7 54.5 54.3 54.0 53.7 53.5 69.6 130.1 130.0 133.9 140 135 130 125 120 115 110 105 100 95 f1 90 85 80 75 70 65 60 55 50 13 C NMR spectrum of 2b
-164.90-72.71-45 -55-65 -75-85 -95-105 -115 f1-125 -135-145 -155-165 -175 19 F NMR spectrum of 2b
m-bis(perfluoro-tert-butoxylmethyl)benzene (2c) 1 H NMR spectrum of 2c 81.53 81.24 80.94 80.65 80.35 80.05 71.82 71.80 129.76 128.75 127.57 125.62 122.71 119.81 116.88 54.54 54.27 54.00 53.73 53.46 136.40 140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 13 C NMR spectrum of 2c
-72.54-164.90-45 -55-65 -75-85 -95-105 -115-125 -135-145 -155-165 -175 19 F NMR spectrum of 2c
p-bis(perfluoro-tert-butoxylmethyl)benzene (2d) 4.06 4.00 5.07 7.41 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 1 H NMR spectrum of 2d 13 C NMR spectrum of 2d
-164.90-72.66-45 -55-65 -75-85 -95-105 -115-125 -135-145 -155-165 -175 19 F NMR spectrum of 2d
1,3,5-tris(Perfluoro-tert-butoxylmethyl)benzene (2e) 3.00 6.06 7.37 5.10 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 1 H NMR spectrum of 2e 13 C NMR spectrum of 2e
-164.90-72.75-45 -55-65 -75-85 -95-105 -115-125 -135-145 -155-165 -175 19 F NMR spectrum of 2e
1-Bromo-2,4,6-tris(perfluoro-tert-butoxylmethyl)benzene (2f) 1 H NMR spectrum of 2f 13 C NMR spectrum of 2f
-72.68-72.81-164.90-72.65-72.70-72.75 f1-72.80-45 -55-65 -75-85 -95-105 -115 f1-125 -135-145 -155-165 -175 19 F NMR spectrum of 2f
2,6-bis(Perfluoro-tert-butoxylmethyl)pyridine (2g) 1.00 1.96 4.06 7.44 7.42 5.15 7.87 7.85 7.83 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 1 H NMR spectrum of 2g 54.5 54.3 54.0 53.7 53.5 155.3 81.4 81.1 80.8 80.5 80.2 79.9 138.7 125.4 122.5 121.1 119.6 116.6 160 155 150 145 140 135 130 125 120 115 110 105 100 95 90 85 80 75 70 65 60 55 50 45 13 C NMR spectrum of 2g
1.84-164.90 1.00-72.79-45 -55-65 -75-85 -95-105 -115-125 -135-145 -155-165 -175 19 F NMR spectrum of 2g 1 T. Yokoyama, G. R. Wiley, S. I. Miller, J. Org. Chem. 1969, 34, 1859. 2 W. Wenner, J. Org. Chem. 1952, 17, 523. 3 R. E. Benson, R. V. Lindsay Jnr., B. C. Anderson, J. Org. Chem. 1959, 81, 4253. 4 Y. Yamagiwa, Y. Koreishi, S. Kiyozumi, M. Kobayashi, T. Kamikawa, Bull. Chem. Soc. Jpn. 1996, 69, 3317. 5 D. M. Tal, S. J. D. Karlish, Tetrahedron. 1995, 51, 3823.