One-Pot Preparation of Aroylsilanes by Reductive Silylation of Methyl Benzoates

REFERENCES

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• 4g: 1H NMR (δ): 0.37 (9H, s); 3.93 (3H, s); 7.54 (1H, td, J = 8 Hz); 7.97 (1H, dt, J = 8 Hz); 8.18 (1H, dt, J = 8Hz); 8.49 (1H, td, J = 2 Hz). 13C (δ): -1.8 (Si(CH3)3); 52.1 (m-CO2Me); 128.6, 128.7, 130.4, 130.7, 133.0, 141.0 (C6H4); 165.9 (m-CO2Me); 234.4 (COSiMe3). B.p./ mm Hg: 77–78 °C/ 0.2 mm Hg. Mass spectra, m/z: 236 (M+, 4), 221 (18), 205 (11), 193 (36), 177 (30), 163(5), 104 (78), 73(100). HRMS, m/z: Found 237.0939 (MH+); Calc. 237.0947 (MH+)
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• 4h: 1H NMR (δ): 0.36 (9H, s); 3.92 (3H, s); 7.83 (2H, td, J = 8 Hz); 8.12 (2H, td, J = 8 Hz). 13C (δ): -1.5 (Si(CH3)3); 52.4 (p-CO2Me); 127.1, 129.9, 133.3, 143.9 (C6H4); 166.3 (p-CO2Me); 235.9 (COSiMe3). M.p. 43–44 °C. Mass spectra, m/z: 236 (M+, 0.4), 235 (0.9), 221 (6), 205 (2), 193 (18), 177 (32), 163(3), 104 (37), 73(100). HRMS, m/z: Found 237.0956 (MH+); Calc. 237.0947 (MH+)
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• 5: 1H NMR (δ): 0.29 (9H, s); 7.87 (4H, d, J = 9 Hz); 9.99 (1H, s). 13C (δ): -1.8 (Si(CH3)3); 127.5, 129.9, 138.3, 144.5 (C6H4); 191.6 (p-COH); 235.9 (CO). Mass spectra, m/z: 206 (M+, 18), 191 (7), 177 (39), 163 (55), 133 (6), 119 (2), 105 (9), 73 (100). HRMS, m/z: Found 207.0844 (MH+); Calc. 207.0841 (MH+)
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• 6a: 1H NMR (δ): 0.41 (6H, s); 5.87 (1H, dd, Jtrans = 20 Hz, Jgem = 3 Hz); 6.12 (1H, dd, Jcis = 15 Hz, Jgem = 3 Hz); 6.36 (1H, dd, Jtrans = 20 Hz, Jcis = 15 Hz); 7.41–7.51 (3H, m); 7.84 (2H, dt, J = 7 Hz). 13C NMR (δ): -3.5 (Si(CH3)2); 127.7, 128.5, 132.8, 134.4 (C6H4); 135.8, 141.3 (CHCH2); 233.9 (CO). Mass spectra, m/z: 190 (M+, 36), 189 (100), 175 (34), 163 (6), 147 (13), 135 (11), 121 (14), 105 (18), 85 (52), 77 (41), 59 (41), 51 (16). HRMS, m/z: Found 191.0889 (MH+); Calc. 191.0892 (MH+)
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• 6b: 1H NMR (δ): 0.36 (6H, s); 2.41 (3H, s); 5.83 (1H, dd, Jtrans = 20 Hz, Jgem = 3 Hz); 6.09 (1H, dd, Jcis = 15 Hz, Jgem = 3 Hz); 6.29 (1H, dd, Jtrans = 20 Hz, Jcis = 15 Hz); 7.18–7.32 (3H, m); 7.63 (1H, dd, J = 7 Hz). 13C NMR (δ): -3.7 (Si(CH3)2); 20.7 (o-CH3); 125.7, 130.7, 131.9, 134.2 (m, C6H4); 135.6, 141.6 (CHCH2); 239.7 (CO). Mass spectra, m/z: 204 (M+, 12), 203 (16), 189 (100), 119 (31), 91 (36), 85 (83), 75 (22), 65 (21), 59 (90). HRMS, m/z: Found 205.1046 (MH+); Calc. 205.1049 (MH+)
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• 4a: 1H NMR (δ): 0.36 (9H, s); 7.42–7.54 (3H, m); 7.81 (2H, d, J = 7 Hz). 13C NMR (δ): -1.4 (Si(CH3)3); 235.7(CO). Mass spectra, m/z: 178 (M+, 18), 105 (13), 73 (100)
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• 4b: 1H NMR (δ): 0.35 (9H, s); 7.36–7.48 (2H, m); 7.67–7.72 (2H, m). 13C NMR (δ): -1.5 (Si(CH3)3); 234.3 (CO). Mass spectra, m/z: 214 (M+2, 0.5), 213 (M+1, 0.6), 212 (M+, 1), 177 (23), 73 (100)
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• 4c: 1H NMR (δ): 0.34 (9H, s); 2.38 (3H, s); 7.30–7.36 (2H, m), 7.59–7.65 (2H, m). 13C NMR (δ): -1.4 (Si(CH3)3); 21.3 (m-CH3); 235.7 (CO). Mass spectra, m/z: 192 (M+, 1), 91 (17), 73 (100)
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• 4d: 1H NMR (δ): 0.29 (9H, s); 2.39 (3H, s); 7.18–7.33 (3H, 7.53–7.56 (1H, m). 13C NMR (δ): -1.7 (Si(CH3)3); 20.6 (o-CH3); 242.2 (CO). Mass spectra, m/z: 192 (M+, 8), 91 (15), 73 (100)
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• 4e: 1H NMR (δ): 0.34 (9H, s); 2.38 (3H, s); 7.25 (2H, d, J = 8 Hz); 7.72 (2H, d, J = 8 Hz). 13C NMR (δ): -1.3 (Si(CH3)3); 21.7 (p-CH3); 234.9 (CO). Mass spectra, m/z: 192 (M+, 3), 91 (24), 73 (100)
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• 4f: 1H NMR (δ): 0.35 (9H, s); 1.32 (9H, s); 7.47 (2H, d, J = 8 Hz); 7.78 (2H, d, J = 8 Hz). 13C NMR (δ): -1.3 (Si(CH3)3); 31.1, 35.5 (C(CH3)3); 234.8 (CO). Mass spectra, m/z: 234 (M+, 1), 177 (100), 73 (65)
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• Neyer , G. and Prakash , G. K. S. unpublished results. Methyl 4-formyl-benzoate (60 mmol, 10 g), trimethylorthoformate (70 mmol, 77 mL), and methanol (30 mL) were mixed with Dowex strongly acidic ion-exchange resin (1 g), which was prewashed with methanol and dried. The reaction mixture was refluxed for two hours, filtered and solvent evaporated. The resulting mixture was dissolved in ether (50 mL), and the solvent evaporated to yield colorless methyl-4-dimethoxyformyl-benzoate crystals
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• Acetone (50 mL) was added to the reaction mixture after quenching with ammonium chloride. The aqueous solution was refluxed for two hours, and worked up similarly to give m-chloro acylsilane
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