Regiospecific Normal Diels–Alder Reaction of trans-1,2-Biscoumarinylethenes

Kailas K. Sanap; Shriniwas D. Samant

doi:10.1055/s-0031-1290454

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(15): 2189-2194
DOI: 10.1055/s-0031-1290454

letter

Regiospecific Normal Diels–Alder Reaction of trans-1,2-Biscoumarinylethenes

Kailas K. Sanap

Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai 400 019, India, Fax: +91(22)33611020 eMail: samantsd@yahoo.com eMail: sd.samant@ictmumbai.edu.in

,

Shriniwas D. Samant*

Department of Chemistry, Institute of Chemical Technology, N. Parekh Marg, Matunga, Mumbai 400 019, India, Fax: +91(22)33611020 eMail: samantsd@yahoo.com eMail: sd.samant@ictmumbai.edu.in

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Abstract

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Abstract

The reaction of different 7,8-substituted coumarin 4-acetic acids with 7-diethylaminocoumarin-3-carbaldehyde in the presence of piperidine in methanol gives 1,2-biscoumarinylethenes. These compounds undergo regiospecific Diels–Alder reactions at their electron-rich diene components C₃–C₄–C₁₀–C₉, with electron-deficient dienophiles. The feasibility of normal electron-demand Diels–Alder reactions could be explained on the basis of the HOMO–LUMO gap. All the compounds are new and are intensely colored.

Key words

coumarins - cycloaddition reaction - Diels–Alder reaction - 3,4-annulated coumarin - regiospecific reaction

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Referenzen

References and Notes

1a Geissman TA. The Chemistry of Flavonoid Compounds . Pergamon Press; Oxford: 1962
1b Harborne JB. The Flavonoids: The Advances in Research since 1980 . Chapman and Hall; London: 1988
1c Harborne JB. The Flavonoids: The Advances in Research since 1980 . Chapman and Hall; London: 1994

2 Rastogi RP, Mehrotra BN In Compendium of Indian Medicinal Plants . Vol. 3. Rastogi RP. Central Drug Research Institute and Publications and Information Directorate; Lucknow/New Delhi: 1993: 273
3 Izquierdo ME. F, Granados JQ, Mir VM, Martinez MC. L. Food Chem. 2000; 70: 251
4 Kuznetsova NA, Kaliya OL. Usp. Khim. 1992; 61: 1243

5a Jones G, Jackson WR, Choi C, Bergmark WR. J. Phys. Chem. 1985; 89: 294
5b Koefod RS, Mann KR. Inorg. Chem. 1989; 28: 2285
5c Jagtap AR, Satam VS, Rajule RN, Kanetkar VR. Dyes Pigm. 2009; 82: 84

6a Lee MT, Yen CK, Yang WP, Chen HH, Liao CH, Tsai CH, Chen CH. Org. Lett. 2004; 6: 1241
6b Yu TZ, Zhang P, ZhaoY L, Zhang H, Meng J, Fan DW. Org. Electron. 2009; 10: 653

7a Dorlars A, Schellhammer CW, Schroeder J. Angew. Chem., Int. Ed. Engl. 1975; 14: 665
7b Keskin SS, Aslan N, Bayrakceken N. Spectrochim. Acta, Part A 2009; 72: 254
7c Kido J, Iizumi Y. Appl. Phys. Lett. 1998; 73: 2721

8a Moylan CR. J. Phys. Chem. 1994; 98: 13513
8b Painelli A, Terenziani F. Synth. Met. 2001; 124: 171

9a Hassan MA, Shiba SA, Harb NS, Abou-El-Regal MK, El-Metwally SA. Synth. Commun. 2002; 32: 679
9b Raji Reddy C, Kiranmai N, Johny K, Pendke M, Naresh P. Synthesis 2009; 399

10a Prabhakar M, Reddy GN, Srinu G, Manjulatha K, Prasad JV, Kumar SP, Srinivas O, Iqbal J, Kumar KA. Synlett 2010; 947
10b Girotti R, Marrocchi A, Minuti L, Piermatti O, Pizzo F, Vaccaro L. J. Org. Chem. 2006; 71: 70
10c Ballerini E, Minuti L, Piermatti O. J. Org. Chem. 2010; 75: 4251
10d Amantini D, Fringuelli F, Piermatti O, Pizzo F, Vaccaro L. J. Org. Chem. 2003; 68: 9263
10e Jung ME, Allen DA. Org. Lett. 2009; 11: 757
10f Flores-Larios IY, Lizbeth-Lopez G, Martínez-Martínez FJ, González J, García-Báez EV, Cruz A, Padilla-Martínez II. Molecules 2010; 15: 1513
10g Amantini D, Fringuelli F, Pizzo F. J. Org. Chem. 2002; 67: 7238

11a Yasuda M, Kishi T, Goto C, Satoda H, Nakabayashi K, Minami T, Shima K. Tetrahedron Lett. 1992; 33: 6465
11b Minami T, Matsumoto Y, Nakamura S, Koyanagi S, Yamaguchi M. J. Org. Chem. 1992; 57: 167
11c Mustafa A, Kamel M. J. Am. Chem. Soc. 1955; 77: 1828
11d Mustafa A, Kamel M, Allam MA. J. Am. Chem. Soc. 1956; 78: 4692
11e El-Shafei A, Fadda AA, Abdel-Gawad II, Youssif EH. E. Synth. Commun. 2009; 39: 2954

12a Bodwell GJ, Pi Z, Pottie IR. Synlett 1999; 477
12b Pottie IR, Nandaluru PR, Bodwell GJ. Synlett 2011; 2245
12c Pottie IR, Nandaluru PR, Benoit WL, Miller DO, Dawe LN, Bodwell GJ. J. Org. Chem. 2011; 76: 9015
12d Nandaluru PR, Bodwell GJ. Org. Lett. 2012; 14: 310

13 Wu J.-S, Liu W.-M, Zhuang X.-Q, Wang F, Wang P.-F, Tao S.-L, Zhang X.-H, Wu S, Lee S.-T. Org. Lett. 2007; 9: 33
14 Laskowski SC, Clinton RO. J. Am. Chem. Soc. 1950; 72: 3987
15 Soliman AY, El-Kafrawy AF, Mohamed FK, Baker HM, Abdel-Gawad AM. Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem. 1991; 30: 477
16 Kudale AA, Kendall J, Miller DO, Collins JL, Bodwell GJ. J. Org. Chem. 2008; 73: 8437
17 Experimental Procedure for 3a Compound 2a (0.218 g, 1 mmol) and piperidine (0.085 g, 1 mmol) were stirred in MeOH (6 mL) for 15 min and 1 (0.245 g, 1 mmol) was added slowly at r.t. After complete consumption of 1, the precipitated solid was collected by filtration and washed with a small quantity of cold MeOH followed by H₂O to remove traces of piperidine. Solid 3a was washed with EtOAc. The second crop of 3a was obtained from the filtrate; the filtrate was evaporated to obtain a sticky mass which was purified by column chromatography on silica gel using toluene–EtOAc (70:30, v/v); orange solid; 64% yield; mp 231–233 °C. IR (neat): ν = 1698, 1609, 1575, 1513, 1352, 1252, 1192, 1132 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 1.25 (t, 6 H, 2 × CH₃, J = 7.5 Hz), 2.46 (s, 3 H, CH₃), 3.47 (q, 4 H, 2 × CH₂, J = 7.5 Hz), 6.49 (s, 1 H, C3H), 6.51 (d, 1 H, C8′H, J = 2.0 Hz), 6.65 (dd, 1 H, C6′H, J = 2.0, 9.0 Hz), 7.13–7.15 (m, 2 H, C5′H and C8H), 7.20 (d, 1 H, C10H, J = 15.5 Hz), 7.37 (d, 1 H, C6H, J = 8.5 Hz), 7.77 (d, 1 H, C5H, J = 8.5 Hz), 7.79 (s, 1 H, C4′H), 7.99 (d, 1 H, C9H, J = 15.5 Hz). MS: m/z = 402.57 [M + 1]. Anal. Calcd (%) for C₂₅H₂₃NO₄ (401.45): C, 74.79; H, 5.77; N, 3.49. Found: C, 74.58; H, 5.88; N, 3.52.
18 Experimental Procedure for 16a Compound 3a (0.401 g, 1 mmol) and 11 (0.256 g, 2 mmol) were refluxed in dioxane (6 mL) for 2 h. After complete consumption of 3a, the solution was cooled to r.t. and was evaporated to obtain a sticky mass which was purified by column chromatography on silica gel using toluene–EtOAc (80:20, v/v); buff solid; 85% yield; mp 269–270 °C. IR (neat): δ = 2975, 1702, 1594, 1519, 1251, 1128 cm^–1. ¹H NMR (300 MHz, CDCl₃): δ = 1.23 (t, 6 H, 2 × CH₃, J = 6.9 Hz), 2.50 (s, 3 H, CH₃), 3.50 (q, 4 H, 2 × CH₂, J = 6.9 Hz), 3.59 (d, 2 H, C10H, J = 7.2 Hz), 4.29 (t, 1 H, C9H, J = 7.2 Hz), 6.44 (d, 1 H, C8′H, J = 2.1 Hz), 6.64 (dd, 1 H, C6′H, J = 2.1, 8.7 Hz), 7.22 (s, 1 H, C8H), 7.24 (d, 1 H, C6H, J = 7.8 Hz), 7.38 (d, 1 H, C5′H, J = 8.7 Hz), 7.58 (d, 1 H, C5H, J = 8.1 Hz), 7.93 (s, 1 H, C4′H). ¹³C NMR (300 MHz, CDCl₃): δ = 12.4 (2 × CH₃), 22.0 (ArCH₃), 28.3 (C10), 36.9 (C9), 42.3 (C8), 45.1 (2 × CH₂), 46.5 (C7), 97.0 (C8′), 107.5 (C3′), 108.9 (CN), 109.2 (CN), 109.4 (C10b), 109.7 (2 × CN), 109.8 (C6′), 111.6 (C4a′), 114.6 (C6a), 117.7 (C4), 124.8 (C2), 127.2 (C1), 130.1 (C5′), 142.8 (C4′), 147.4 (C3), 152.0 (C7′), 152.3 (C10a), 152.9 (C4a′), 156.5 (C8a′), 157.1 (C2′), 161.5 (C6). MS: m/z = 530.46 [M + 1]. Anal. Calcd (%) for C₃₁H₂₃N₅O₄ (529.55): C, 70.31; H, 4.38; N, 13.23. Found: C, 70.48; H, 4.47; N, 13.19.

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