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1 Supporting Information Solvent-free synthesis of 1,4-disubstituted 1,2,3-triazoles using a low amount of Cu(PPh 3 ) 2 O 3 complex Dong Wang, a Li, Mingming Zhao, Weilin Shi, Chaowei Ma and Baohua Chen* State Key Laboratory of Applied Organic Chemistry Lanzhou University, Lanzhou ,P.R.of China; Key Laboratory of onferrous Metal Chemistry and Resources Utilization of Gansu Province, Lanzhou ,P.R.of China. chbh@lzu.edu.cn Table of Contents 1. General Remarks S2 2. Spectral data of the compounds S2-S10 3. References S H and 13 C MR spectra of the products S12-S65

2 1. General Remarks: Flash column chromatography was performed using silica gel ( mesh). Analytical thin-layer chromatography was performed using glass plates pre-coated with mesh silica gel impregnated with a fluorescent indicator (254 nm). 1 H MR spectra were recorded on 300 or 400 MHz and 13 C MR spectra were recorded on 75 or 100 MHz using TMS as internal standard. IR spectra were recorded on a FT-IR spectrometer and only major peaks are reported in cm -1. Melting points were determined on a microscopic apparatus. All new products were further characterized by ESI HRMS and IR; copies of 1 H MR and 13 C MR spectra are provided. Commercially available reagents were used without further purification. 2. Spectral data of the compounds: 3a 1-benzyl-4-phenyl-1H-1,2,3-triazole (3a) 1 : 3a was isolated as a white solid (yield 96%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 7.79(t, J=4.4 Hz, 2H), 7.66(s, 1H), (m, 5H), (m, 3H), 5.54(s, 2H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , F 3b 1-benzyl-4-(4-fluorophenyl)-1H-1,2,3-triazole (3b) 1 : 3b was isolated as a white solid (yield 80%). mp: o C. 1 H MR (300 MHz, CDCl 3 ): δ H ( m, 2H), 7.63(s, 1H), (m, 3H), (m, 2H), (m, 2H), 5.55(s, 2H). 13 C MR (75 MHz, CDCl 3 ): δ C , , , , , , , , , , , , ,

3 O 2 3c 1-benzyl-4-(4-nitrophenyl)-1H-1,2,3-triazole (3c) 2 : 3c was isolated as a yellow solid (yield 81%), mp: 168 o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.24(d, J=8.8 Hz, 2H), 7.96(d, J=8.8 Hz, 2H), 7.81(s, 1H), (m, 5H), 5.60(s, 2H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , O 3d 1-benzyl-4-(4-(pentyloxy)phenyl)-1H-1,2,3-triazole (3d): 3d was isolated as a white solid (yield 81%), mp: o C. IR (cm -1 ): , , , , , , , , , , , , H MR (300 MHz, CDCl 3 ): δ H (m, 2H), 7.56(s, 1H), (m, 3H), (m, 2H), 6.91(d, J=9.0 Hz, 2H), 5.53(s, 2H), 3.96(t, J=6.5 Hz, 2H), (m, 2H), (m, 4H), 0.93(t, J=7.1 Hz, 3H). 13 C MR (75 MHz, CDCl 3 ): δ C , , , , , , , , , , 68.01, 54.11, 28.90, 28.14, 22.41, ESI HRMS: calcd. for C 20 H 23 3 O [M+H] + : , found: e 2-(1-benzyl-1H-1,2,3-triazol-4-yl)pyridine (3e) 2 : 3e was isolated as a white solid (yield 86%). mp: o C. 1 H MR (300 MHz, CDCl 3 ): δ H ( m, 1H), (m, 1H), 8.06(s, 1H), (m, 1H), (m, 5H), (m, 1H), 5.56(s, 2H). 13 C MR (75 MHz, CDCl 3 ): δ C , , , , , , , , , , ,

4 S 3f 1-benzyl-4-(thiophen-3-yl)-1H-1,2,3-triazole (3f) 3 : 3f was isolated as a white solid (yield 99%). mp: o C. 1 H MR (300 MHz, CDCl 3 ): δ H ( m, 1H), 7.57(s, 1H), (m, 1H), (m, 4H), (m, 2H), 5.51(s, 2H). 13 C MR (75 MHz, CDCl 3 ): δ C , , , , , , , , , , g Fc 1-benzyl-4-ferrocenyl-1H-1,2,3-triazole (3g) 4 : 3g was isolated as a golden yellow solid (yield 70%). mp: o C. 1 H MR (300 MHz, CDCl 3 ): δ H 7.36(d, J=8.1 Hz, 4H), 7.25(t, J=3.6 Hz, 2H), 5.51(s, 2H), 4.69(s, 2H), 4.27(s, 2H), 4.05(s, 5H). 13 C MR (75 MHz, CDCl 3 ): δ C , , , , , , 75.41, 69.52, 68.61, 66.55, h 1-benzyl-4-butyl-1H-1,2,3-triazole (3h) 5 : 3h was isolated as a white solid (yield 94%). mp: o C. 1 H MR (300 MHz, CDCl 3 ): δ H (m, 3H), 7.25(t, J=3.9 Hz, 2H), 7.20(s, 1H), 5.48(s, 2H), 2.68(t, J=7.8 Hz, 2H), (m, 2H), (m, 2H), 0.91(t, J=7.4 Hz, 3H). 13 C MR (75 MHz, CDCl 3 ): δ C , , , , , , 53.82, 31.40, 25.29, 22.20, i

5 1-benzyl-4-tert-butyl-1H-1,2,3-triazole (3i) 5 : 3i was isolated as a white solid (yield 95%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H (m, 3H), (m, 2H), 7.17(s, 1H), 5.48(s, 2H), 1.32(s, 9H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , 53.83, 30.68, j 1-benzyl-4-octyl-1H-1,2,3-triazole (3j) 1 : 3j was isolated as a white solid (yield 98%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H (m, 3H), 7.25(t, J=3.8 Hz, 2H), 7.20(s, 1H), 5.48(s, 2H), 2.68(t, J=7.8 Hz, 2H), (m, 2H), (m, 10H), 0.87(t, J=6.8 Hz, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , 53.81, 31.70, 29.28, 29.18, 29.13, 29.06, 25.61, 22.52, OH 3k 2-(1-benzyl-1H-1,2,3-triazol-4-yl)propan-2-ol (3k) 6 : 3k was isolated as a white solid (yield 95%). mp: o C. 1 H MR (300 MHz, CDCl 3 ): 7.41(s, 1H), (m, 3H), (m, 2H), 5.44(s, 2H), 3.61(s, 1H), 1.58(s, 6H). 13 C MR (75 MHz, CDCl 3 ): δ C , , , , , , 68.19, 53.81, O 2 4a 1-(4-nitrobenzyl)-4-phenyl-1H-1,2,3-triazole (4a) 7 : 4a was isolated as a yellow solid (yield 98%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.19(d, J=8.8 Hz, 2H), (m, 3H), (m, 4H), (m, 1H), 5.68(s, 2H). 13 C MR

6 (100 MHz, CDCl 3 ): δ C , , , , , , , , , , b 1-pentyl-4-phenyl-1H-1,2,3-triazole (4b) : 4b was isolated as a white solid (yield 94%). mp: o C. IR (cm -1 ): , , , , , , , , , H MR (400 MHz, CDCl 3 ): δ H 7.84(t, J=4.2 Hz, 2H), 7.75(s, 1H), 7.41(t, J=7.6 Hz, 2H), (m, 1H), 4.36(t, J=7.2 Hz, 2H), (m, 2H), (m, 4H), 0.89(t, J=6.8 Hz, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , 50.29, 29.93, 28.48, 21.99, ESI HRMS: calcd. for C 13 H 17 3 [M+H] + : , found: c 1-octyl-4-phenyl-1H-1,2,3-triazole (4c) 9 : 4c was isolated as a white solid (yield 99%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 7.83(d, J=7.2 Hz, 2H), 7.75(s, 1H), 7.41(t, J=7.6 Hz, 2H), 7.31(t, J=7.4 Hz, 1H), 4.36(t, J=7.2 Hz, 2H), 1.92(t, J=7.0 Hz, 2H), (m, 10H), 0.87(t, J=6.8 Hz, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , 50.29, 31.58, 30.22, 28.92, 28.85, 26.37, 22.47, d 1-dodecyl-4-phenyl-1H-1,2,3-triazole (4d) 10 : 4d was isolated as a white solid (yield 90%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 7.83(d, J=7.2 Hz, 2H), 7.74(s, 1H), 7.42(t, J=7.6 Hz, 2H), 7.32(t, J=7.4 Hz, 1H), 4.38(t, J=7.2 Hz, 2H), (m, 2H), (m, 18H), 0.88(t, J=6.8 Hz, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , 50.40, 31.86, 30.32,

7 29.66, 29.56, 29.47, 29.35, 29.28, 28.98, 26.48, 22.64, e 1,4-diphenyl-1H-1,2,3-triazole (4e) 11 : 4e was isolated as a white solid (yield 98%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.20(s, 1H), 7.92(d, J=7.2 Hz, 2H), 7.80(t, J=4.6 Hz, 2H), (m, 2H), (m, 3H), 7.36(t, J=7.4 Hz, 1H). 13 C MR (100 MHz, d6-dmso): δ C , , , , , , , , , Cl 4f 1-(2-chlorophenyl)-4-phenyl-1H-1,2,3-triazole (4f) 8 : 4f was isolated as a brown solid (yield 98%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.19(s, 1H), 7.92(t, J=4.2 Hz, 2H), (m, 1H), (m, 1H), (m, 4H), 7.35(t, J=7.4 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , , Cl 4g 1-(3-chlorophenyl)-4-phenyl-1H-1,2,3-triazole (4g) : 4g was isolated as a white solid (yield 99%). mp: o C. IR (cm -1 ): , , , , , , , , , H MR (400 MHz, CDCl 3 ): δ H 8.19(s, 1H), 7.91(t, J=4.2 Hz, 2H), 7.84(t, J=1.8 Hz, 1H), 7.71(d, J=8.0 Hz, 1H), (m, 5H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , , ESI HRMS: calcd. for C 14 H 10 3 Cl [M+H] + : , found:

8 Cl 4h 1-(4-chlorophenyl)-4-phenyl-1H-1,2,3-triazole (4h) 12 : 4h was isolated as a yellow solid (yield 57%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.16(s, 1H), 7.91(d, J=7.2 Hz, 2H), 7.76(d, J=8.8 Hz, 2H), 7.53(d, J=8.8 Hz, 2H), 7.47(t, J=7.4 Hz, 2H), 7.39(d, J=7.2 Hz, 1H), 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , O 2 4i 1-(2-nitrophenyl)-4-phenyl-1H-1,2,3-triazole (4i) 13 : 4i was isolated as a yellow solid (yield 45%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.06(t, J=3.4 Hz, 2H), 7.89(d, J=7.2 Hz, 2H), (m, 1H), (m, 2H), 7.45(t, J=7.4 Hz, 2H), 7.37(t, J=7.4 Hz, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , , O 2 4j 1-(3-nitrophenyl)-4-phenyl-1H-1,2,3-triazole (4j) 14 : 4j was isolated as a yellow solid (yield 81%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.67(s, 1H), (m, 3H), (m, 2H), 7.78(t, J=8.2 Hz, 1H), ?(m, 2H), (m, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , , Br

9 4k 1-(2-bromophenyl)-4-phenyl-1H-1,2,3-triazole (4k) : 4k was isolated as a yellow solid (yield 97%). mp: o C. IR (cm -1 ): , , , , , , , , , H MR (400 MHz, CDCl 3 ): δ H 8.15(s, 1H), 7.92(t, J=4.2 Hz, 2H), (m, 1H), (m, 1H), (m, 3H), (m, 2H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , , ESI HRMS: calcd. for C 14 H 10 3 Br [M+H] + : , found: , I 4l 1-(2-iodophenyl)-4-phenyl-1H-1,2,3-triazole (4l) : 4l was isolated as a white solid (yield 81%). mp: o C. IR (cm -1 ): , , , , , , , H MR (400 MHz, CDCl 3 ): δ H 8.09(s, 1H), 8.08(t, J=4.4 Hz, 1H), 7.94(t, J=4.4 Hz, 2H), (m, 4H), 7.38(t, J=7.4 Hz, 1H), (m, 1H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , , ESI HRMS: calcd. for C 14 H 10 3 I [M+H] + : , found: O 4m 1-(2-methoxyphenyl)-4-phenyl-1H-1,2,3-triazole (4m) 12 : 4m was isolated as a brown oil (yield 99%). 1 H MR (400 MHz, CDCl 3 ): δ H 8.31(s, 1H), 7.91(t, J=4.2 Hz, 2H), (m, 1H), (m, 3H), 7.32(t, J=7.2 Hz, 1H), (m, 2H), 3.86(s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , , , O 4n 1-(4-methoxyphenyl)-4-phenyl-1H-1,2,3-triazole (4n) 12 : 4n was isolated as a white

10 solid (yield 99%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 8.10(s, 1H), 7.90(t, J=4.2 Hz, 2H), (m, 2H), (m, 2H), 7.35(t, J=3.6 Hz, 1H), 7.01(d, J=8.8 Hz, 2H), 3.85(s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , o 4-phenyl-1-o-tolyl-1H-1,2,3-triazole (4o) 12 : 4o was isolated as a yellow solid (yield 85%). mp: o C. 1 H MR (400 MHz, CDCl 3 ): δ H 7.96(s, 1H), 7.92(t, J=4.4 Hz, 2H), (m, 7H), 2.26(s, 3H). 13 C MR (100 MHz, CDCl 3 ): δ C , , , , , , , , , , , , p 1-(3,4-dimethylphenyl)-4-phenyl-1H-1,2,3-triazole (4p): 4p was isolated as a white solid (yield 98%). mp: o C. IR (cm -1 ): , , , , , , , , , , , H MR (300 MHz, CDCl 3 ): δ H 8.13(s, 1H), 7.89(t, J=4.4 Hz, 2H), 7.54(d, J=1.5 Hz, 1H), (m, 3H), (m, 1H), 7.23(t, J=5.6 Hz, 1H), 2.31(s, 3H), 2.29(s, 3H). 13 C MR (75 MHz, CDCl 3 ): δ C , , , , , , , , , , , , 19.80, ESI HRMS: calcd. for C 16 H 15 3 [M+H] + : , found:

11 References 1. K. Kamata, Y. akagawa, K. Yamaguchi and. Mizuno, J. Am. Chem. Soc., 2008, 130, C. Richardson, C. M. Fitchett, F. R. Keene, P. J. Steel, Dalton Trans., Y. Angell and K. Burgess, Angew. Chem., Int. Ed., 2007, 46, Y.-B. Zhao, Z.-Y. Yan and Y.-M. Liang, Tetrahedron Letters., 2006, 47, Candelon, D. Lastécouères, A. K. Diallo, J. R. Aranzaes, D. Astruc and J.-M. Vincent, Chem. Commun., 2008, 6, B. H. Lipshutz and B. R. Taft, Angew. Chem., Int. Ed., 2006, 45, P. Appukkuttan, W. Dehaen, V. V. Fokin and E. V. Eycken, Org. Lett., 2004, 6, A. Sarkar, T. Mukherjee and S. Kapoor, J. Phys. Chem. C, 2008, 112, T. Miao and L. Wang, Synthesis., 2008, P. H. Lia and L. Wang, Letters in Organic Chemistry, 2007, 4, Z. X. Wang and H. L. Qin, Chem. Commun., 2003, C.-Z. Tao, X. Cui, J. Li, A.-X. Liu, L. Liu and Q.-X. Guo, Tetrahedron Letters, 2007, 48, B. Saha, S. Sharma, D. Sawant and B. Kundu, Tetrahedron, 2008, 64, Z.-X. Wang and H.-L. Qin, Chem. Commun., 2003, 19, 2450

12 3a

14 3b

16 3c

18 3d

20 3e

22 3f

24 3g

26 3h

28 3i

30 3j

32 3k

34 4a

36 4b

38 4c

40 4d

42 4e

44 4f

46 4g

48 4h

50 4i

52 4j

54 4k

56 4l

58 4m

60 4n

62 4o

64 4p