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DOI: 10.1055/s-0030-1260766
Facile Synthesis of Spiropyrans from Chromene Hemiacetal Esters and Bifunctional Nucleophiles
Publikationsverlauf
Publikationsdatum:
26. Mai 2011 (online)
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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.
Key words
spiropyran - tandem reaction - hemiacetal ester - chromene - bifunctional nucleophile
- Supporting Information for this article is available online:
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References and Notes
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.
8
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.