# Design, Synthesis and Antifungal Activity of Novel Benzoylcarbamates Bearing a Pyridine Moiety
## 2 Materials and Methods
### Synthesis
#### 2.1.4 General Procedure for the Synthesis of Substituted Benzoylcarbamates **(4a-4j)**  
To a mixture of benzoyl isocyanate freshly prepared as above (9 mmol) in dry tetrahydrofuran (12 mL), a solution of 3,3-Dimethyl-1-(pyridin-3-yl)butan-2-ol (1.62 g, 9 mmol) in dry tetrahydrofuran (20 mL) was slowly added under stirring. After stirring at room temperature for 3 h, the solvent was evaporated to yield a crude product. Further purification was performed by silica gel chromatography with ethyl acetate/petroleum ether (\(V\):\(V\) = 1:2) as eluent, and target compounds were obtained as white solids. **3,3-Dimethyl-1-(pyridin-3-yl)butan-2-yl benzoylcarbamate (4a)**. Yield 82%, m.p. 153-154\({}^{\circ}\)C. \({}^{1}\)H NMR (CDCl\({}_{3}\)) \(\delta\) 1.07 (s, 9H, C(CH\({}_{3}\))\({}_{3}\)), 2.78-2.84 (m, 1H, CH\({}_{2}\)), 2.98 (d, \(J\) = 14.0 Hz, 1H, CH\({}_{2}\)), 5.01 (q, \(J\) = 8.0 Hz, 1H, CH), 7.19-7.72 (m, 7H, Ar-H), 8.38 (bs, 1H, NH), 8.45 (s, 2H, Py-H). \({}^{13}\)C NMR (CDCl\({}_{3}\)) \(\delta\) 165.50, 151.35, 150.36, 147.77, 136.72, 133.67, 133.28, 132.69, 128.61, 127.82, 123.48, 83.02, 35.04, 33.35, 25.96. IR (KBr)\(v_{\rm max}\) 3285 (N-H), 1753 (C=O of carbamate), 1683 (C=O of benzoyl), 1397 and 1371 (C-H of \(t\)-butyl) cm\({}^{-1}\). Analysis calculated for C\({}_{19}\)H\({}_{22}\)N\({}_{2}\)O\({}_{3}\): C 69.92, H 6.79, N 8.58; found: C 69.65, H 6.54, N 8.72%. **3,3-Dimethyl-1-(pyridin-3-yl)butan-2-yl (2-methylbenzoyl)carbamate (4b)**. Yield 87%, m.p. 157-158\({}^{\circ}\)C. \({}^{1}\)H NMR (CDCl\({}_{3}\)) \(\delta\) 1.03 (s, 9H, C(CH\({}_{3}\))\({}_{3}\)), 2.31 (s, 3H, CH\({}_{3}\)), 2.72-2.79 (m, 1H, CH\({}_{2}\)), 2.97 (dd, \(J\) = 2.4, 11.6 Hz, 1H, CH\({}_{2}\)), 4.98 (q, \(J\) = 8.4 Hz, 1H, CH), 7.18-7.61 (m, 6H, Ar-H), 8.17 (bs, 1H, NH), 8.31 (s, 1H, Py-H), 8.43 (s, 1H, Py-H). \({}^{13}\)C NMR (CDCl\({}_{3}\)) \(\delta\) 168.26, 150.83, 150.22, 147.65, 136.74, 136.29, 134.72, 133.42, 130.99, 126.91, 125.71, 123.58, 82.38, 35.02, 33.23, 25.95, 19.98. IR (KBr)\(v_{\rm max}\) 3285 (N-H), 1770 (C=O of carbamate), 1700 (C=O of benzoyl), 1395 and 1365 (C-H of \(t\)-butyl) cm\({}^{-1}\). Analysis calculated for C\({}_{20}\)H\({}_{24}\)N\({}_{2}\)O\({}_{3}\): C 70.57, H 7.11, N 8.23; found: C 70.75, H 7.04, N 8.12%. **3,3-Dimethyl-1-(pyridin-3-yl)butan-2-yl (3-methylbenzoyl)carbamate (4c)**. Yield 84%, m.p. 147-148\({}^{\circ}\)C. \({}^{1}\)H NMR (CDCl\({}_{3}\)) \(\delta\) 1.07 (s, 9H, C(CH\({}_{3}\))\({}_{3}\)), 2.38 (s, 3H, CH\({}_{3}\)), 2.78-2.84 (m, 1H, CH\({}_{2}\)), 2.98 (dd, \(J\) = 2.4, 12.0 Hz, 1H, CH\({}_{2}\)), 5.01 (q, \(J\) = 8.0 Hz, 1H, CH), 7.19-7.64 (m, 6H, Ar-H), 8.31 (bs, 1H, NH), 8.39 (d, \(J\) = 4.8 Hz, 1H, Py-H), 8.45 (d, \(J\) = 1.6 Hz, 1H, Py-H). \({}^{13}\)C NMR (CDCl\({}_{3}\)) \(\delta\) 164.93, 151.34, 150.77, 148.19, 143.87, 136.79, 130.45, 129.61, 127.93, 123.65, 83.47, 35.28, 33.61, 26.19, 21.75. IR (KBr)\(v_{\rm max}\) 3273 (N-H), 1757 (C=O of carbamate), 1679 (C=O of benzoyl), 1396 and 1365 (C-H of \(t\)-butyl) cm\({}^{-1}\). Analysis calculated for C\({}_{20}\)H\({}_{24}\)N\({}_{2}\)O\({}_{3}\): C 70.57, H 7.11, N 8.23; found: C 70.81, H 7.14, N 8.06%. **3,3-Dimethyl-1-(pyridin-3-yl)butan-2-yl (4-methylbenzoyl)carbamate (4d)**. Yield 82%, m.p. 151-153\({}^{\circ}\)C. \({}^{1}\)H NMR (CDCl\({}_{3}\)) \(\delta\) 1.06 (s, 9H, C(CH\({}_{3}\))\({}_{3}\)), 2.40 (s, 3H, CH\({}_{3}\)), 2.78-2.84 (m, 1H, CH\({}_{2}\)), 2.98 (dd, \(J\) = 2.4, 12.0 Hz, 1H, CH\({}_{2}\)), 5.00 (q, \(J\) = 8.0 Hz, 1H, CH), 7.22-7.62(m, 6H, Ar-H), 8.11 (bs, 1H, NH), 8.42-8.46 (m, 2H, Py-H). \({}^{13}\)C NMR (CDCl\({}_{3}\)) \(\delta\) 164.75, 151.16, 150.59, 148.01, 143.69, 136.61, 130.27, 129.43, 127.75, 123.47, 83.29, 35.10, 33.43, 26.01, 21.57. IR (KBr)\(v_{\rm max}\) 3280 (N-H), 1740 (C=O of carbamate), 1678 (C=O of benzoyl), 1396 and 1368 (C-H of \(t\)-butyl) cm\({}^{-1}\). Analysis calculated for C\({}_{20}\)H\({}_{24}\)N\({}_{2}\)O\({}_{3}\): C 70.57, H 7.11, N 8.233,3-Dimethyl-1-(pyridin-3-yl)butan-2-yl (2-methoxybenzoyl)carbamate (4e). Yield 80%; m.p.