Preparation of Benz[b]Indeno[1,2-e]Pyran-11(6H)-Ones and Benz[b]Indeno[1,2-e]Thiopyran-11(6H)-One from Dilithiated 2-Indanone and Lithiated Methyl Salicylates or Lithiated Methyl Thiosalicylate

References

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• Melting points were obtained with a Mel-Temp II melting point apparatus in open capillary tubes and are uncorrected. b. Combustion analyses for C and H were performed by Quantitative Technologies, Inc., P.O. Box 470, Salem Industrial Park, Bldg. 5, Whitehouse, NJ 08888.
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• Fourier Transform infrared spectra (paraffin oil mulls) were obtained with a Nicolet Impact 410 FT-IR. k Proton and 13C NMR spectra were obtained with a Varian Associates Mercury Oxford 300 MHZ, nuclear magnetic resonance spectrometer, and chemical shifts are recorded in δ ppm downfield from an internal tetramethylsilane (TMS) standard. NMR data: all compounds were soluble in CDCl3: Compd. No.;1H NMR spectra; 13C NMR spectra. 3. 1H NMR: δ 3.94 (s, 2H, CH2), 7.26–7.71, 8.24–8.39 (m, 8H, ArH). 13C NMR: δ 41.1, 122.3, 125.3, 126.8, 127.9, 129.0, 129.4, 130.0, 130.3, 131.7, 137.2, 138.2, 142.4, 160.5, 176.0, and 180.4. 4. 1H NMR: δ 3.93 (s, 3H, ArOCH3), 3.94 (s, 2H, CH2), 6.96–7.05, 7.25–7.47, 8.24–8.30 (m, 7H, ArH). 13C NMR: δ 37.0, 56.1, 100.5, 100.6, 114.3, 118.9, 121.2, 122.9, 123.9, 125.9, 127.7, 134.3, 138.7, 158.3, 163.7, 171.5, and 174.1. 5. 1H NMR: δ 4.04 (s, 2H, CH2), 4.07 (s, 3H, ArOCH3), 7.21–7.50, 7.94–7.97, 8.27–8.29 (m, 6H, ArH). 13C NMR: δ 41.5, 61.0, 118.3, 121.6, 127.2, 128.2, 129.4, 130.4, 132.0, 142.6, 154.4, and 180.2. 6. 1H NMR: δ 3.95 (s, 2H, CH2), 7.24–7.64, 8.22–8.31 (m, 7H, ArH). 13C NMR: δ 41.4, 124.2, 125.7, 127.2, 128.2, 130.0, 130.3, 130.5, 132.0, 135.7, 137.6, 138.4, 142.2, 159.0, 176.4 and 177.3. 7. 1H NMR: δ 3.95 (s, 2H, CH2), 7.26–7.78, 8.21–8.48 (m, 7H, ArH). 13C NMR: δ 37.4, 119.2, 120.5, 121.8, 123.4, 124.3, 127.6, 127.8, 128.1, 129.3, 134.5, 136.4, 138.3, 155.7, 172.4, and 173.2. 8. 1H NMR: δ 3.96 (s, 2H, CH2), 7.26–7.48, 7.92–8.25, and 8.68–8.69 (m, 7H, ArH). 13C NMR: δ 36.8, 89.1, 120.0, 121.2, 122.6, 123.6, 125.7, 126.3, 127.4, 133.8, 134.9, 137.7, 141.3, 155.6, 171.7, and 172.4. 9. 1H NMR: δ 2.45 (s, 3H, ArCH3), 3.88 (s, 2H, CH2), 7.24–7.47, 8.11–8.24 (m, 8H, ArH). 13C NMR: δ 25.3, 41.0, 122.0, 125.0, 126.7, 127.8, 128.6, 129.6, 129.9, 131.6, 138.21, 138.25, 139.3, 142.5, 158.9, 175.8, and 178.4. 10. 1H NMR: δ 4.04 (s, 2H, CH2), 7.26–7.67, 8.55–8.57, 8.71–8.73 (m, 8H, ArH). 13C NMR: δ 41.4, 122.9, 123.1, 125.8, 126.6, 127.3, 128.8, 130.8, 132.3, 133.7, 139.0, 140.6, 153.4, and 177.2.
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• Chemicals were purchased from Aldrich Chemical Co. The methyl esters for 6–8 were routinely prepared from either 5-chloro-, 5-bromo-, or 5-iodo-, salicylic acids, excess methanol and sulfuric acid. For example, methyl 5-bromosalicylate was prepared by treating 5-bromosalicylic acid (25 g) with 300 – 350 mL of methanol, 5 mL of conc. sulfuric acid, and heating the solution under reflux with stirring overnight (12 – 16 hr.). Speedy purification could be accomplished by reduction in volume (ca., 25 – 50 mL), followed by a single recrystallization of the solid product from methanol.
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