Facile Synthesis of Spiropyrans from Chromene Hemiacetal Esters and Bifunctional Nucleophiles

Abstract

Facile synthesis of several new kinds of spiropyrans has been accomplished through the condensation of chromene hemi­acetal esters with bifunctional nuclephiles, in which previously nonpractical amination and amidation processes help each other and all become practical processes of the corresponding tandem reactions.

spiropyran - tandem reaction - hemiacetal ester - chromene - bifunctional nucleophile

References and Notes

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<A NAME="RW05211ST-7">7</A>

CCDC 800884 contains the supplementary crystallographic data of spiropyran 3i for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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Synthetic Procedure for Spiropyrans 3
A solution of (1R,2R)-1,2-diphenylethane-1,2-diamine (1h, 42.5mg, 0.2 mmol) and hemiacetal esters 2a (67.7mg, 0.2 mmol) in CH₂Cl₂ (2 mL) was stirred at reflux for 3 d. The mixture was concentrated, and the residue was purified
by column chromatography over silica gel to afford 2H-chromene-piperazin-2-one spiropyran 3c (85.1 mg) in 85% yield as a single diastereomer. White solid; mp 136-137 ˚C. [α]_D ^²4 +101.27 (c 2.0, MeCO₂Et). ^¹H NMR (300 MHz, CDCl₃): δ = 7.43-7.05 (m, 18 H), 5.95 (s, 2 H), 4.67 (s, 2 H), 2.98 (br s, 1 H), 1.18 (s, 9 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 167.2, 148.1, 144.1, 138.0, 137.9, 137.8, 137.6, 129.0, 128.6, 128.5, 128.4, 128.4, 128.3, 128.2, 128.1, 127.7, 126.6, 123.3, 120.4, 120.2, 117.0, 86.9, 65.8, 58.6, 34.3, 31.4. FT-IR (KBr): 3350, 3033, 2361, 1693, 1489, 1245, 921, 700 cm^-¹. Anal. Calcd for C₃₄H₃₂N₂O₂: C, 81.57; H, 6.44; N, 5.60. Found: C, 81.43; H, 6.67; N, 5.82.