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Electronic supplementary materials Mendeleev Commun., 2017, 27, 565‒566

Direct introduction of cyano group on furoxan ring

Lorenzo Annaratone, Stefano Guglielmo and Konstantin Yu. Chegaev

Chemistry

Anhydrous sodium sulfate (Na2SO4) was used as drying agent for the organic phases.

Organic solvents were removed under reduced pressure at 30 °C. Synthetic-purity solvents dichloromethane, DMF and 40–60 petroleum ether (PE) were used. Dry DMF was obtained through storage over 4Å molecular sieves. The progress of the reactions was followed by thin-layer chromatography (TLC) on 5 × 20 cm plates Merck Kieselgel 60 F254, with a layer thickness of 0.20 mm.

4-Cyano-3-phenylfuroxan (2). To a solution of 3-phenyl-4-phenylsulfonylfuroxan (300 mg, 1.00 mmol) in dry DMF (10 ml), KCN (65 mg, 1.00 mmol) was added in one portion followed by 18-crown-6 (260 mg, 1.00 mmol). The mixture was stirred at room temperature for 1 h and then was poured into cold water (30 ml) and extracted with CH2Cl2 (2 × 25 ml). The organic phase was

washed with water (20 ml), brine (20 ml), dried and evaporated. The obtained yellow oil was purified by flash chromatography (eluent PE : CH2Cl2 = 8 : 2) to give the target cyano derivative as

a white solid. Yield 98 mg (58%). Analytically pure sample was obtained by crystallization from hexane. Mp 84-85 °C (C6H14), lit.1 mp 81 °C. 1H NMR (300 MHz, CDCl3)  (ppm): 7.99 – 8.02 (m,

2H), 7.60 – 7.62 (m, 3H). 13C NMR (75 MHz, CDCl

3) : 133.0 (4C, Fx), 132.1 (CH of C6H5), 129.7

(2CH of C6H5), 126.4 (2CH of C6H5), 119.6 (C of C6H5), 112.6 (3C, Fx), 108.4 (CN).

3-Cyano-4-phenylfurazan (8). To a solution of 3-phenyl-4-phenylsulfonylfurazan (290 mg, 1.00 mmol) in dry DMF (10 ml) KCN (65 mg, 1.00 mmol) was added in one portion followed by 18-crown-6 (260 mg, 1.00 mmol). The mixture was stirred at room temperature for 18 h, then poured into cold water (30 ml) and extracted with CH2Cl2 (2 × 25 ml). The organic phase was

washed with water (20 ml), brine (20 ml), dried and evaporated. The obtained yellow oil was purified by flash chromatography (eluent PE : CH2Cl2 = 9 : 1) to give the target cyano derivative as

a white solid. Yield 86 mg (50%). Analytically pure sample was obtained by crystallization from hexane. Mp 45-46 °C (C6H14), lit.2 mp 40-41 °C. 1H NMR (300 MHz, CDCl3)  (ppm): 8.00 – 8.04

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(m, 2H), 7.57 – 7.68 (m, 3H). 13C NMR (75 MHz, CDCl3) : 154.4 (3C, Fz), 132.4 (CH of C6H5),

130.6 (4C, Fz), 129.7 (2CH of C

6H5), 127.7 (2CH of C6H5), 122.5 (C of C6H5), 108.3 (CN).

Table S1 Attempts to extend the procedure for differently substituted 4-phenylsulfonyl furoxans / furazans.

N+ N O R" N (O-)n N+ N O R" (O-)n R' CN -R' R'' n Conditions Results SO2Ph SO2Ph 1 KCN / DMF / 18-crown-6 / rt decomposition SO2Ph SO2Ph 1 nBu4N+CN- / CH2Cl2 / rt decomposition SO2Ph SO2Ph 1 nBu4N+CN- / CH2Cl2 / -15 °C decomposition SO2Ph SO2Ph 1 nBu4N+CN- / CH2Cl2 / -78 °C no reaction

SO2Ph OEt 1 KCN / DMF / 18-crown-6 / rt decomposition

SO2Ph CH3 1 KCN / DMF / 18-crown-6 / rt decomposition NO2 CH3 1 KCN / DMF / 18-crown-6 / rt decomposition SO2Ph SO2Ph 0 KCN / DMF / 18-crown-6 / rt decomposition SO2Ph SO2Ph 0 nBu4N+CN- / CH2Cl2 / rt decomposition SO2Ph SO2Ph 0 nBu4N+CN- / CH2Cl2 / -15 °C decomposition SO2Ph SCH2Ph 0 KCN / DMF / 18-crown-6 / rt decomposition

SO2Ph OEt 0 KCN / DMF / 18-crown-6 / rt decomposition

SO2Ph CH3 0 KCN / DMF / 18-crown-6 / rt decomposition

Supplementary Part References

1. R. Fruttero, B. Ferrarotti, A. Serafino and A. Gasco, Liebigs Ann. Chem., 1990, 4, 335. 2. G. Ponzio, Gazz. Chim. Ital., 1931, 61, 943.

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