Abstract
A representative spiro[benzopyran-isoxazole], 3′-(3,4-dimethoxyphenyl)-N,N-diethyl-4-methyl-4′H-spiro[2H-1-benzopyran-2,5′-isoxazol]-7-amine 3a, was submitted for single crystal X-ray analysis. It has been prepared by the condensation–cyclization of dilithiated C(α),O-3′,4′-dimethoxyacetophenone oxime with a substituted coumarin, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one. This results from the 1,2-carbonyl addition, Claisen type, of the dilithiated oxime with this coumarin ester carbonyl to afford C-acylated intermediates that were not isolated, but were acid cyclized to the spiro[benzopyran-isoxazoles], a new spiro heterocyclic system. There was no evidence for Michael-type 1,4-addition found during this initial investigation. An indication that the experimental multiple anion procedure is general, has been the preparation of two additional spiro(benzopyran-isoxazoles) 3b and 3c. Crystals of C24H28N2O4 3a are triclinic, \(p\bar{1}\), a = 9.161(2) Å, b = 9.716(2) Å, c = 12.869(3) Å, α = 75.84(3)°, β = 81.03(3)°, γ = 73.96(3)°, Z = 2, V = 1062.5(4) Å3, R 1 = 0.0539 and wR 2 = 0.1366 for reflections with I > 2σ(I).
Graphical Abstract
X-ray crystal analysis confirmed the structure of 3′-(3,4-dimethoxyphenyl)-N,N-diethyl-4-methyl-4′H-spiro(2H-1-benzopyran-2,5′-isoxazol)-7-amine prepared by the condensation–cyclization of dilithiated C(α),O-3′,4′-dimethoxyacetophenone oxime with a substituted coumarin, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one.
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Acknowledgments
We wish to thank the following sponsors for support: the Research Corporation, the Summer Undergraduate Research Forum (SURF) of the College of Charleston, and the Howard Hughes Medical Institute (HHMI) along with earlier Grants from the National Science Foundation (CHE # 9708014 and # 0212699) for Research at Undergraduate Institutions (NSF-RUI), and the United States Department of Agriculture (NRICGP # 2003-35504-1285).
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Metz, C.R., Radke, J.L., Shuler, W.G. et al. Preparation of Spiro[Benzopyran-Isoxazoles] from the Condensation–Cyclization of Oxime 1,4-Dianions with Select Coumarins. J Chem Crystallogr 44, 401–406 (2014). https://doi.org/10.1007/s10870-014-0529-z
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DOI: https://doi.org/10.1007/s10870-014-0529-z