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G. Ya. Remennikov V. V. Pirozhenko S. I. Vdovenko S. A. Kravchenko 《Chemistry of Heterocyclic Compounds》1998,34(1):104-110
We have studied the reaction of isomeric 7-and 5-methoxyfuroxano[3,4-d]pyrimidines with carbanions of some CH acids. We have shown that regardless of the position of the substituent in the pyrimidine ring, nucleophilic attack occurs regioselectively at the C(7) atom. As a result, we have obtained the products of substitution at the methoxy group, and also anionic complexes and covalent adducts.For Communication 12 see [1].Institute of Bioorganic Chemistry and Petrochemistry, National Academy of Sciences of Ukraine, Kiev 253660. Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 34, No. 1, pp. 112–119, January, 1998. 相似文献
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Sergey I. Vdovenko Igor I. Gerus Natalia V. Lutenko Valery P. Kukhar Jacek Wjcik 《Journal of Molecular Structure》2007,840(1-3):125-132
Spatial structure of six β-substituted enones, with common structure R1O–CR2CH–COCF3, were R1 = C2H5, R2 = H (ETBO); R1 = R2 = CH3 (TMPO); R1 = C2H5, R2 = C6H5 (ETPO); R1 = C2H5, R2 = 4- O2NC6H4 (ETNO); R1 = C2H5, R2 = C(CH3)3 (ETDO) were investigated by 1H and 19F NMR, infrared spectroscopy and AM1 calculations. NMR spectra revealed that enones (MBO), (ETBO) and (TMPO) are exclusively (3E) isomers, whereas in (ETPO), (ETNO) and especially in (ETDO) the percentage of (3Z) isomers is significant and depends on the nature of solvents. Conformational behaviour of studied enones are determined by the rotation around of CC double bond, C–C and C–O single bonds (correspondingly trifluoroacetyl and alkoxy groups), and (EZZ) conformer being the most stable in all cases. IR spectra revealed that with the exception of (ETDO) (EZZ) conformer is most populated in all cases. Bulky substituents like phenyl or tert-butyl group at β-position of enone result in the equilibrium mainly between (EZZ) and (ZZZ) forms, whereas β-hydrogen and β-methyl substituents determine the equilibrium between (EZZ) and (EEZ) or (EZE) conformers. 相似文献
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Sergey I. Vdovenko Igor I. Gerus Valery P. Kukhar 《Journal of Physical Organic Chemistry》2007,20(3):190-200
The kinetics of the reaction of β‐substituted β‐alkoxyvinyl trifluoromethyl ketones R1O‐CR2?CH‐COCF3 ( 1a – e ) [( 1a ), R1?C2H5, R2?H; ( 1b ), R1?R2?CH3; ( 1c ), R1?C2H5, R2?C6H5; ( 1d ), R1?C2H5, R2?V?pNO2C6H4; ( 1e ), R1?C2H5, R2?C(CH3)3] with four aliphatic amines ( 2a – d ) [( 2a ), (C2H5)2NH; ( 2b ), (i‐C3H7)2NH; ( 2c ), (CH2)5NH; ( 2d ), O(CH2CH2)2NH] was studied in two aprotic solvents, hexane and acetonitrile. The least reactive stereoisomeric form of ( 1a – d ) was the most populated ( E‐s‐Z‐o‐Z ) form, whereas in ( 1e ), the more reactive form ( Z‐s‐Z‐o‐Z ) dominated. The reactions studied proceeded via common transition state formation whose decomposition occurred by ‘uncatalyzed’ and/or ‘catalyzed’ route. Shielding of the reaction centre by bulky β‐substituents lowered abruptly both k′ (‘uncatalyzed’ rate constant) and k″ (‘catalyzed’ rate constant) of this reaction. Bulky amines reduced k″ to a greater extent than k′ as a result of an additional steric retardation to the approach of the bulky amine to its ammonium ion in the transition state. An increase in the electron‐withdrawing ability of the β‐substituent increased ‘uncatalyzed’ k′ due to the acceleration of the initial nucleophile attack (k1) and ‘uncatalyzed’ decomposition of transition state (k2) via promoting electrophilic assistance (through transition state 8 ). The amine basicity determined the route of the reaction: the higher amine basicity, the higher k3/k2 ratio (a measure of the ‘catalyzed’ route contribution as compared to the ‘uncatalyzed’ process) was. ‘Uncatalyzed’ route predominated for all reactions; however in polar acetonitrile the contribution of the ‘catalyzed’ route was significant for amines with high pKa and small bulk. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
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