ABSTRACT
We report the synthesis of a series of novel stilbene-based (St) Fischer base analogs of leuco-triarylmethane (LTAM) dyes by treating Fischer base with (E)-4-styrylbenzaldehyde derivatives. All St-LTAM molecules examined herein are characterized by 1D and 2D NMR. They were found to exhibit ZE configuration and isomerize to their diastereomers EE and ZZ in 2-3 h. They exhibit type I behavior of diastereomeric isomerization.
ABSTRACT
The solid-state structures and unequivocal stereochemistries of isomeric pyridine-based leuco-triarylmethane (LTAM) dyes 2,2'-(2-(pyridin-4 or 3-yl)propane-1,3-diylidene)bis(5-chloro-1,3,3-trimethylindoline) derivatives were established by X-ray crystallography. Surprisingly, the EE isomer was formed for the 4-pyridinyl compound, whereas the 3-pyridinyl compound formed ZE isomers. In addition, the latter have a so-called three-bladed propeller conformation, whereas the former possess a Y-shaped conformation. These pyridine-based LTAM compounds stack to form a dimer, adopting either an orthorhombic, with Pcmn space group, or monoclinic crystal system with P21/n space group in the crystal unit cell.
Subject(s)
Coloring Agents/chemistry , Coloring Agents/chemical synthesis , Pyridines/chemistry , Pyridines/chemical synthesis , Crystallography, X-Ray , Dimerization , Isomerism , Models, Molecular , Molecular Conformation , Spectrophotometry, UltravioletABSTRACT
The (1)H and (13)C NMR spectra of the novel heterocyclic Leuco-TAM dyes, (2Z, 2'E)-2,2'-(2-phenyl propane-1,3-diylidene) bis(1,3,3-trimethylindoline) derivatives 1-4 as precursors of triarylmethane (TAM)(+) (Malachite Green FB-analog) dyes were completely assigned by 1D and 2D NMR experiments, including DEPT, COSY, HSQC, HMBC, and NOESY. Especially, the diastereotopic gem-dimethyl protons at the C3 and C3' positions of the FB rings were definitively assigned. The (Z,E) isomers adopt the energetically favored three-bladed propeller conformation in solution.
Subject(s)
Coloring Agents/chemistry , Heterocyclic Compounds/chemistry , Indoles/chemistry , Magnetic Resonance Spectroscopy/methods , Magnetic Resonance Spectroscopy/standards , Rosaniline Dyes/chemistry , Carbon Isotopes , Molecular Conformation , Protons , Reference Standards , Solutions/chemistry , StereoisomerismABSTRACT
Fifteen chalcones and three thiazolidinedione (TZD) chalcones were prepared to evaluate their peroxisome proliferator-activated receptor-gamma (PPAR-gamma) ligand-binding activities. Among the three TZDs, one compound possessed PPAR-gamma transactivation potential, while the others showed antagonistic activity against PPAR-gamma transactivation. Among the chalcones, compound 5 was the most potent, and structure-activity relationship studies indicated that a methoxyl group in position C-4 and hydroxyl group in position C-4' or 5' in chalcone plays a key role in determining the potency of PPAR-gamma activation.
Subject(s)
Chalcone/analogs & derivatives , PPAR gamma/metabolism , Thiazolidinediones/chemistry , Thiazolidinediones/metabolism , Chalcone/chemistry , Chalcone/metabolism , Chalcones , Indicators and Reagents , Ligands , Luciferases/chemistry , Reverse Transcriptase Polymerase Chain Reaction , Structure-Activity Relationship , Tetrazolium Salts , Thiazoles , TransfectionABSTRACT
The (1)H and (13)C NMR spectra of dicondensed indolinobenzospiropyrans as precursors of thermo- and photochromic spiropyrans, DC1-DC5, were completely assigned. Especially, the (1)H assignment and coupling characteristics of the diastereotopic protons at the carbon-3 position of the benzopyran rings were achieved by conducting (1)H-(1)H COSY and nOe experiments. The dihedral angles (theta(1), theta(2) and theta(3)) calculated from the experimental values of the vicinal coupling constants ((3)J) of DC5 are in good agreement with the observed values in the solid state. All of the carbons in the DC dye molecules were investigated through a combination of heteronuclear 2D-shift correlation spectroscopy (HETCOR) and DEPT135.
Subject(s)
Benzene Derivatives/chemistry , Benzopyrans/chemistry , Indoles/chemistry , Magnetic Resonance Spectroscopy , Benzene Derivatives/metabolism , Benzopyrans/chemical synthesis , Benzopyrans/metabolism , Carbon Isotopes/chemistry , Hot Temperature , Hydrogen/chemistry , Indoles/metabolism , Luminescence , Molecular Structure , Nitro Compounds , Photochemistry , Reference StandardsABSTRACT
(1)H and (13)C NMR spectra of symmetric and asymmetric bis-spiropyrans, Series 1-3, were completely assigned. Especially, the (1)H assignment of asymmetric spiropyrans was achieved by utilizing (1)H-(1)H COSY and nOe experiments. All of the carbons in the dye molecules were investigated through a combination of heteronuclear 2D-shift correlation spectroscopy (HETCOR), together with an attached proton test (APT).
Subject(s)
Benzopyrans/chemistry , Magnetic Resonance Spectroscopy/methods , Magnetic Resonance Spectroscopy/standards , Benzopyrans/radiation effects , Carbon Isotopes , Deuterium , Indoles , Molecular Conformation , Nitro Compounds , Photochemistry , Protons , Reference StandardsABSTRACT
The therapeutic potential of aldose reductase inhibitors for the prevention of the secondary complications of diabetes has been extensively reported. On the other hand, the hyperaggregability of platelets in diabetic patients has also been reported as a cause of chronic diabetic complications. The purpose of this study was to develop new compounds with these dual effects from pyridyloxy- or phenoxylphenoxyalkanate synthesized derivatives and examine the effect of their structure-activity relationships on the inhibition of rat lens aldose reductase (RLAR) as well as on platelet aggregation. 2-[4-(2,6-dichloro-3-methyl-phenoxy)-3-nitro-phenoxy]-propionic acid (3) exhibited the most potent inhibitory effect (IC(50) = 3.0 +/- 0.21 microM), comparable to tetramethylene glutaric acid (IC(50) = 6.1 +/- 0.2 microM), which is used as a positive control on RLAR, and showed potent inhibitory activities on rat platelet aggregation induced by ADP and collagen (IC(50) = 0.093 +/- 0.01 and 0.032 +/- 0.01 microM, respectively) comparable with aspirin (IC(50) = 0.15 +/- 0.05 and 0.047 +/- 0.01 microM, respectively), used as a positive control.