TY - JOUR
T1 - From solid state photodimers of ethyl coumarin-3-carboxylate to their alcoholysis derivatives. A supramolecular study
AU - Ayala-Hurtado, S.
AU - Flores-Larios, I. Y.
AU - Padilla-Martínez, I. I.
AU - Martínez-Martínez, F. J.
AU - García-Báez, E. V.
AU - Cruz, A.
AU - Höpfl, H.
PY - 2007/12
Y1 - 2007/12
N2 - The solid state photodimerization of ethyl coumarin-3-carboxylate and its 6-Cl and 6-Br (1a-c) derivatives as well as the methyl and ethyl alcoholysis derivatives of ethyl coumarin-3-carboxylate photodimer are reported in the context of crystal engineering. Ethyl coumarin-3-carboxylates photodimerize topochemically to form anti head-to-tail stereoisomers (2a-c). The extent of lactone methanolysis of 2a depends on the boiling temperature of the solvent to produce 2-(2-hydroxyphenyl)-3-oxo-8bH-4-oxa-cyclobuta[a]naphthalene-1,1,2a- tricarboxylic acid 1,2a-diethyl ester 1-methyl ester (3a) and 2,4-bis-[(2-hydroxyphenyl]cyclobutane-1,1,3,3-tetracarboxylic acid diethyl ester dimethyl ester (4a) in 1:2 proportion, whereas the ethanolysis of 2a only yields 2-(2-hydroxyphenyl)-3-oxo-8bH-4-oxa-cyclobuta[a]naphthalene-1,1,2a- tricarboxylic acid triethyl ester (5a). The molecular structure of 2a-c and 3-5a were elucidated by 1H and 13C NMR spectroscopy. Also the molecular and supramolecular structures of 2a,b and 3,4a were studied by X-ray diffraction. Most of the C-H⋯X (X = O, Ph), π⋯π and dipolar interactions in the photodimers 2a,b and derivative 3a are preserved from the corresponding original coumarin monomers. Thus the supramolecular structure of ethyl coumarin-3-carboxylate is conserved through this group of compounds as if they would have a "supramolecular memory". [image omitted].
AB - The solid state photodimerization of ethyl coumarin-3-carboxylate and its 6-Cl and 6-Br (1a-c) derivatives as well as the methyl and ethyl alcoholysis derivatives of ethyl coumarin-3-carboxylate photodimer are reported in the context of crystal engineering. Ethyl coumarin-3-carboxylates photodimerize topochemically to form anti head-to-tail stereoisomers (2a-c). The extent of lactone methanolysis of 2a depends on the boiling temperature of the solvent to produce 2-(2-hydroxyphenyl)-3-oxo-8bH-4-oxa-cyclobuta[a]naphthalene-1,1,2a- tricarboxylic acid 1,2a-diethyl ester 1-methyl ester (3a) and 2,4-bis-[(2-hydroxyphenyl]cyclobutane-1,1,3,3-tetracarboxylic acid diethyl ester dimethyl ester (4a) in 1:2 proportion, whereas the ethanolysis of 2a only yields 2-(2-hydroxyphenyl)-3-oxo-8bH-4-oxa-cyclobuta[a]naphthalene-1,1,2a- tricarboxylic acid triethyl ester (5a). The molecular structure of 2a-c and 3-5a were elucidated by 1H and 13C NMR spectroscopy. Also the molecular and supramolecular structures of 2a,b and 3,4a were studied by X-ray diffraction. Most of the C-H⋯X (X = O, Ph), π⋯π and dipolar interactions in the photodimers 2a,b and derivative 3a are preserved from the corresponding original coumarin monomers. Thus the supramolecular structure of ethyl coumarin-3-carboxylate is conserved through this group of compounds as if they would have a "supramolecular memory". [image omitted].
KW - Carbonyl-carbonyl interactions
KW - Chlorine-carbonyl interactions
KW - Ethyl coumarin-3-carboxylate
KW - Pi⋯pi and C-H⋯pi interactions
KW - Solid state photodimers
UR - http://www.scopus.com/inward/record.url?scp=36949020335&partnerID=8YFLogxK
U2 - 10.1080/10610270701414245
DO - 10.1080/10610270701414245
M3 - Artículo
SN - 1061-0278
VL - 19
SP - 629
EP - 640
JO - Supramolecular Chemistry
JF - Supramolecular Chemistry
IS - 8
ER -