Supporting Information

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1 Supporting Information Antonio Palumbo Piccionello, Annalisa Guarcello, Silvestre Buscemi, icolò Vivona, and Andrea Pace* Dipartimento di Chimica Organica "E. Paternò", Università degli Studi di Palermo, Viale delle Scienze - Parco d'orleans II, I Palermo, Italy. pace@unipa.it Contents Instrumentation and Chemicals S2 Optimization of reaction conditions for hydrazinolysis of 4a.S2 MR Spectra....S4-S25 S1

2 Instrumentation and Chemicals Melting points were determined on a hot-stage apparatus and are uncorrected. FT-IR spectra were registered in ujol mull. 1 -MR and 13 C-MR spectra were recorded at 300Mz and 62.5 Mz, respectively, using TMS as an internal standard. Flash chromatography was performed by using silica gel ( mm) and mixtures of ethyl acetate and petroleum ether (fraction boiling in the range of C) in various ratios. Compounds 4a,b 1, 4c, 2, 4d, 3 4e, 4 and 4f-h, 1 were obtained as previously reported. For compounds 8a-d, 5 8g-i 5 and 8f 6, spectroscopic data matched those reported in cited literature. Optimization of reaction conditions for hydrazinolysis of 4a. To a stirred solution of oxadiazole 4a (1 mol, g) in the appropriate solvent (10 ml for MeO, DCM or TF; 2 ml for DMF) was added hydrazine hydrate (40 mmol, 1.94 ml) and the mixture was kept under conditions reported in Table 1. After completion of reaction (TLC) the mixture was evaporated, the residue treated with water, neutralized with Cl 1M and extracted with EtOAc, which was dried and evaporated, and the residue was chromatographed giving 3(5)-amino-5(3)- phenyl-1,2,4-triazole 8a [Mp C (lit )]. Results are reported in Table 1. 1) Eloy, F.; Deryckere, A.; Van Overstraeten, A. Bull. Soc. Chim. Bel. 1969, 78, ) Palumbo Piccionello, A.; Pace, A.; Buscemi, S.; Vivona,. Org. Lett. 2009, 11, ) Westphal, G. ; Schmidt, R. Z. Chem. 1974, 14, 94 (Chem, Abstr., 1974, 81, 13443). 4) Choi, P.; Rees, C. W.; Smith, E.. Tetrahedron Lett. 1982, 23, ) Dolzhenko, A. V.; Pastorin, G.; Dolzhenko, A. V.; Chui, W. K. Tetrahedron Lett. 2009, 50, ) Dolzhenko, A. V.; Dolzhenko, A. V.; Chui, W. K. eterocycles 2007, 71, S2

3 Table 1. Reaction of 3-chloro-5-phenyl-1,2,4-oxadiazole 4a with hydrazine under various conditions. a Ph Cl O 4a 2 2 solvent Ph 2 8a entry 2 2 (equiv.) Solvent Temp. ( C) Time (h) 8a yield (%) b 1 40 MeO reflux DCM reflux TF DMF DMF a Conversion 100%. b Isolated yield. S3

4 MR Spectra F 3 C 4i O Cl Figure S1 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 4i. S4

5 F 3 C 4i O Cl Figure S2 13 C MR (62.5 Mz, DMSO-d 6 ) spectrum of compound 4i. S5

6 4j O Cl Figure S3 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 4j. S6

7 4j O Cl Figure S4 13 C MR (62.5 Mz, DMSO-d 6 ) spectrum of compound 4j. S7

8 O Cl O 4k Figure S5 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 4k. S8

9 O Cl O 4k Figure S6 13 C MR (62.5 Mz, DMSO-d 6 ) spectrum of compound 4k. S9

10 S Cl O 4l Figure S7 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 4l. S10

11 S Cl O 4l Figure S8 13 C MR (62.5 Mz, DMSO-d 6 ) spectrum of compound 4l. S11

12 O Cl 4m Figure S9 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 4m. S12

13 O Cl 4m Figure S10 13 C MR (62.5 Mz, DMSO-d 6 ) spectrum of compound 4m. S13

14 7 O Figure S11 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 7. S14

15 7 O Figure S12 13 C MR (62.5 Mz, DMSO-d 6 ) spectrum of compound 7. S15

16 8a 2 Figure S13 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8a. S16

17 3 C 8b 2 Figure S14 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8b. S17

18 3 CO 8c 2 Figure S15 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8c. S18

19 Cl 8d 2 Figure S16 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8d. S19

20 F 3 C 8e 2 Figure S17 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8e. S20

21 F 3 C 8e 2 Figure S18 13 C MR (62.5 Mz, DMSO-d 6 ) spectrum of compound 8e. S21

22 8f 2 Figure S19 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8f. S22

23 O 8g 2 Figure S20 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8g. S23

24 S 8h 2 Figure S21 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8h. S24

25 8i 2 Figure S22 1 MR (300 Mz, DMSO-d 6 ) spectrum of compound 8i. S25