Supporting Information Amberlyst-15/[Bmim][PF 6 ] Catalyzed Synthesis of C 3 -Symmetric Triarylbenzenes via Cyclotrimerization of Alkynes Kishor V. Wagh and Bhalchandra M. Bhanage Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai 400019, India. Tel.: +91-22-33612603; fax: +91-22-33611020; e-mail: bm.bhanage@gmail.com, bm.bhanage@ictmumbai.edu.in. Table of Contents: 1. General information.......s2 2. General experimental procedure.......... S2 3. Characterization data of compounds..............s3-s6 4. Copies of 1 H NMR and 13 C NMR Spectra......... S7-S16 5. GC-MS chromatogram of crude model reaction mixture...s16 6. References...S17 S1
I. General information: All chemicals and reagents were acquired with their highest purity from various firms and were utilized as it is. GC with capillary column (Elite-1, 30 m 0.32 mm 0.25 µm) and flame ionization detector was used for analysis. GC-MS-QP 2010 instrument (Rtx-17, 30 m 25 mm ID, film thickness 0.25 µm df) (column flow 2 mlmin -1, 80 C to 240 C at 10 C/min rise). The triarylbenzenes were purified by column chromatography on 60-120 mesh silica gel. The 1 H and 13 C NMR spectra were studied at 500 and 100 MHz in CD 3 solvent and TMS as an internal standard. Ionic liquids were prepared as per the procedure from literature. 64 II. Procedure for the synthesis of C 3 -symmetric triarylbenzenes via cyclotrimerization of alkynes: The Amberlyst-15 [H + exchange capacity (4.2 meq/g) and high surface area (42 m 2 /g)] (3 equiv.), [Bmim][PF 6 ] (2 ml) and 1a (3 mmol) was taken in reaction vessel. The reaction at 80 C for 12 h carried out and was monitored by GC/TLC. After the completion of reaction, 5 ml of di-isopropyl ether was used for extraction of product in the ether phase and the extraction procedure (2 5 ml) was repeated. The organic layers containing products were mixed and dried over anhydrous Na 2 SO 4. The crude product was purified on column chromatography [silica gel, 60-120 mesh; PE:EA] and gave the corresponding product 2a in 88% yield. The 2a formation was confirmed by various spectroscopic techniques. The purity of product was studied by GC-MS analysis. Recyclability study: After extraction, the reaction vessel bearing the recovered Amberlyst-15/[Bmim][PF 6 ] was dried at 60 C in vacuo for an hour and then studied with 1a directly for next cycles. S2
3. Characterization data of compounds: (2a) 5'-phenyl-1,1':3',1''-terphenyl White solid: mp 172-174 C (Ref. 1 mp 174.1-174.7 C); 1 H NMR (CD 3, 500 MHz) δ 7.80 (s, 3H), 7.73-7.71 (m, 6H), 7.51-7.48 (t, 6H), 7.42-7.39 (t, 3H). 13 C NMR (CD 3, 100 MHz) δ 142.33, 141.13, 128.84, 127.54, 127.35, 125.17; FTIR (film): 3059, 3017, 1597, 1379, 1077, 856 cm - 1; GC-MS (EI) m/z (%) = 306 (100.0), 227 (4.48), 202 (3.82), 153 (4.3), 144 (5.6), 138 (3.6), 102 (1.2), 77(1.6). Anal. Calcd. for C 24 H 18 : C, 94.08; H, 5.92. Found: C, 94.22; H, 5.44. (2b) 4,4''-dimethyl-5'-(p-tolyl)-1,1':3',1''-terphenyl 2b White solid: mp 176-178 C (lit. 1 mp 175.7-176.9 C); 1 H NMR (CD 3, 500 MHz) δ 7.76 (s, 3H), 7.63-7.61 (d, 6H), 7.32-7.30 (d, 6H), 7.44 (s, 9H). 13 C NMR (CD 3, 100 MHz) δ 142.17, 138.41, 137.26, 129.53, 127.18, 124.57, 21.14; FTIR (film): 3027, 2930, 2861, 1512, 1449, 1109, 810 cm - 1; GC-MS (EI) m/z (%) = 348 (100.0), 333 (26.0), 318 (17.7), 255 (13.3), 239 (12.2), 151 (13.6), 111 (18.2), 97 (25.6). (2d) 4,4''-dimethoxy-5'-(4-methoxyphenyl)-1,1':3',1''-terphenyl White solid: mp 142-143 C (lit. 1 mp 143 C); 1 H NMR (CD 3, 500 MHz) δ 7.59-7.57 (d, 6H), 7.33 (s, 3H), 7.01-6.99 (d, 6H), 2.47 (s, 9H). 13 C NMR (CD 3, 100 MHz) δ 159.13, 141.31, 133.90, 128.25, 122.58, 114.15, 55.35; FTIR (film): 3003, 2926, 1604, 1507, 1281, 1176, 1028, 825 cm - 1. Anal. Calcd. for C 27 H 24 O 3 : C, 81.79; H, 6.10. Found: C, 81.99; H, 6.68. S3
(2e) 4,4''-difluoro-5'-(4-fluorophenyl)-1,1':3',1''-terphenyl White solid: mp 235-237 C (lit. 1 mp 236.5-238 C); 1 H NMR (CD 3, 500 MHz) δ 7.67 (s, 3H), 7.66-7.63 (d, 6H), 7.19-7.16 (d, 6H). 13 C NMR (CD 3, 100 MHz) δ 163.64, 141.52, 137.09, 128.92 (d, J= 7.5Hz), 124.85, 115.86 (d, J= 22.5Hz); FTIR (film): 3045, 2926, 1607, 1505, 1138, 818 cm - 1; GC-MS (EI) m/z (%) = 360 (100.0) [M]+, 361 (M+1, 27.1), 338 (4.1), 318 (2.3), 264 (55.0), 244 (34.8), 180 (6.6), 159 (4.8), 75 (0.8). Anal. Calcd. for C 24 H 15 F 3 : C, 79.99; H, 4.20. Found: C, 79.84; H, 4.20. (2f) 4,4''-dichloro-5'-(4-chlorophenyl)-1,1':3',1''-terphenyl 2f White solid: mp 245-146 C (lit. 1 mp 244.1-244.9 C); 1 H NMR (CD 3, 500 MHz) δ 7.70 (s, 3H), 7.61-7.60 (d, 6H), 7.47-7.45 (d, 6H), 7.42-7.39 (t, 3H). 13 C NMR (CD 3, 100 MHz) δ 141.43, 193.17, 133.92, 129.07, 128.54, 125.01; FTIR (film): 3038, 2923, 1600, 1495, 1091, 1007, 812 cm - 1; Anal. Calcd. for C 24 H 15 3 : C, 70.35; H, 3.69. Found: C, 70.09; H, 3.74. (2g) 3,3''-dichloro-5'-(3-chlorophenyl)-1,1':3',1''-terphenyl 2g White solid: mp 171-172 C (lit. 1 mp 172.4-173 C); 1 H NMR (CD 3, 500 MHz) δ 7.72 (s, 3H), 7.66 (s, 3H), 7.57-7.55 (d, 3H), 7.44-7.37 (m, 6H). 13 C NMR (CD 3, 100 MHz) δ 142.43, 141.28, 134.83, 130.17, 127.82, 127.43, 125.48; FTIR (film): 3059, 2926, 1597, 1383, 1081, 863 cm - 1. Anal. Calcd. for C 24 H 15 3 : C, 70.35; H, 3.69. Found: C, 70.63; H, 3.53. S4
(2h) 2,2''-dichloro-5'-(2-chlorophenyl)-1,1':3',1''-terphenyl 2h White solid: mp 164-166 C (lit. 1 mp 165.1-165.5 C); 1 H NMR (CD 3, 500 MHz) δ 7.60 (s, 3H), 7.52-7.47 (m, 6H), 7.36-7.29 (m, 6H), 13 C NMR (CD 3, 100 MHz) δ 139.92, 138.86, 132.58, 131.59, 130.05, 129.80, 128.72, 126.90; Anal. Calcd. for C 24 H 15 3 : C, 70.35; H, 3.69. Found: C, 70.51; H, 3.16. (2i) 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 2i White solid: mp 260-262 C (lit. 1 mp 260.2-260.9 C); 1 H NMR (CD 3, 500 MHz) δ 7.69 (s, 3H), 7.62-7.60 (d, 6H), 7.55-7.53 (d, 6H), 13 C NMR (CD 3, 100 MHz) δ 141.50, 139.59, 132.04, 128.88, 124.79, 122.10; FTIR (film): 3056, 2930, 1612, 1593, 1484, 1078, 1007, 807 cm - 1. Anal. Calcd. for C 24 H 15 3 : C, 53.08; H, 2.78. Found: C, 52.94; H, 2.52. (2j) 4,4''-dichloro-5'-(4-chloro-3-methylphenyl)-3,3''-dimethyl-1,1':3',1''-terphenyl White solid: mp 218-220 C; 1 H NMR (CD 3, 500 MHz) δ 7.68 (s, 3H), 7.53 (s, 3H), 7.44 (d, 3H), 7.27-7.26 (d, 3H), 2.47 (s, 9H) 13 C NMR (CD 3, 100 MHz) δ 141.50, 139.37, 136.49, 133.99, 131.35, 129.76, 129.48, 125.94, 124.94, 20.25; FTIR (film): 3063, 2926, 1593, 1569, 1397, 1077, 856 cm - 1. Anal. Calcd. for C 27 H 21 3 : C, 71.77; H, 4.68. Found: C, 71.80; H, 4.59. S5
(2k) 1,3,5-tri(naphthalen-2-yl)benzene White solid: mp 221-223 C (lit. 1 mp 222-223 C); 1 H NMR (CD 3, 500 MHz) δ 8.91 (s, 3H), 8.24 (s, 3H), 8.01-7.91 (m, 12H), 7.57-7.51 (m, 6H); FTIR (film): 3024, 3000, 2954, 2835, 1607, 1512, 1291, 1235, 1035, 828 cm - 1. S6
4. Copies of 1 H NMR and 13 C NMR Spectra: (2a) 5'-phenyl-1,1':3',1''-terphenyl 1 H NMR (2a) 5'-phenyl-1,1':3',1''-terphenyl 13 C NMR S7
(2b) 4,4''-dimethyl-5'-(p-tolyl)-1,1':3',1''-terphenyl 1 H NMR 2b (2b) 4,4''-dimethyl-5'-(p-tolyl)-1,1':3',1''-terphenyl 13 C NMR 2b S8
(2d) 4,4''-dimethoxy-5'-(4-methoxyphenyl)-1,1':3',1''-terphenyl 1 H NMR OMe MeO 2d OMe (2d) 4,4''-dimethoxy-5'-(4-methoxyphenyl)-1,1':3',1''-terphenyl 13 C NMR OMe MeO 2d OMe S9
(2e) 4,4''-difluoro-5'-(4-fluorophenyl)-1,1':3',1''-terphenyl 1 H NMR (2e) 4,4''-difluoro-5'-(4-fluorophenyl)-1,1':3',1''-terphenyl 13 C NMR F F 2e F S10
(2f) 4,4''-dichloro-5'-(4-chlorophenyl)-1,1':3',1''-terphenyl 1 H NMR 2f (2f) 4,4''-dichloro-5'-(4-chlorophenyl)-1,1':3',1''-terphenyl 13 C NMR 2f S11
(2g) 3,3''-dichloro-5'-(3-chlorophenyl)-1,1':3',1''-terphenyl 1 H NMR 2g (2g) 3,3''-dichloro-5'-(3-chlorophenyl)-1,1':3',1''-terphenyl 13 C NMR S12
(2h) 2,2''-dichloro-5'-(2-chlorophenyl)-1,1':3',1''-terphenyl 1 H NMR 2h (2h) 2,2''-dichloro-5'-(2-chlorophenyl)-1,1':3',1''-terphenyl 13 C NMR 2h S13
(2i) 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 1 H NMR 2i (2i) 4,4''-dibromo-5'-(4-bromophenyl)-1,1':3',1''-terphenyl 13 C NMR 2i S14
(2j) 4,4''-dichloro-5'-(4-chloro-3-methylphenyl)-3,3''-dimethyl-1,1':3',1''-terphenyl 1 H NMR (2j) 4,4''-dichloro-5'-(4-chloro-3-methylphenyl)-3,3''-dimethyl-1,1':3',1''-terphenyl 13 C NMR S15
(2k) 1,3,5-tri(naphthalen-2-yl)benzene 1 H-NMR 5. GC-MS chromatogram of crude reaction mixture of model reaction S16
6. References 1. Ono, F.; Ishikura, Y.; Tada, Y.; Endo, M.; Sato, T. Efficient conversion of acetophenones into 1,3,5-Triarylbenzenes catalyzed by bismuth(iii) trifluoromethanesulfonate tetrahydrate. Synlett 2008, 15, 2365 2367. S17