Hydration equilibria of 9-acridinecarboxaldehyde

1994 ◽  
Vol 72 (11) ◽  
pp. 2333-2338 ◽  
Author(s):  
Robert A. McClelland ◽  
Pratima Sukhai ◽  
Karen M. Engell ◽  
Poul E. Sorensen
Keyword(s):  
Equilibrium Constants ◽  
Acidity Constant ◽  
Separate Species ◽  
Ph Profile ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Free Aldehyde ◽  
Acidic Conditions ◽  
Acid Catalyzed ◽  
Heterocyclic Aldehydes

Hydration rate constants and equilibrium constants have been obtained for 9-acridinecarboxaldehyde in aqueous solution. Under acidic conditions where the acridine is protonated, signals for the hydrate and free aldehyde forms can be observed as separate species in the 1H NMR spectrum. Integration provides the hydration equilibrium constant[Formula: see text] Using an apparent acidity constant obtained from a spectroscopic titration curve, the rate–pH profile was fitted to provide the hydration constant for the equilibration of the neutral acridines, KH = 0.07. This analysis also provides the acidity constants for the two acridinium ions, the aldehyde with pK = 3.78 and the hydrate with pK = 5.36. A comparison with the 4-pyridinecarboxaldehdye system reveals that the [Formula: see text] ratios for the acridine and pyridine are the same within experimental error, but that the acridine and acridinium aldehydes are 20-fold less hydrated than their pyridine analogs. A comparison with benzaldehydes reveals that, in their reactivities, the two heterocyclic aldehydes behave in a similar manner. Thus, for example, plots of log kH for the acid-catalyzed dehydration and hydrations versus log Kh for the equilibrium hydration show single correlation lines including the points for the benzaldehydes and heterocyclic aldehydes (but not the aliphatic aldehydes).

Vinylogues and heterocyclic analogues of benzylidenemalonaldehydes

1984 ◽  
Vol 49 (11) ◽  
pp. 2613-2619 ◽  
Author(s):  
Zdeněk Arnold ◽  
Dalimil Dvořák ◽  
Vladimír Král
Keyword(s):  
Nmr Spectroscopy ◽  
General Model ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Iminium Salt ◽  
Reaction Intermediate ◽  
Heterocyclic Aldehydes

Nine analogues of benzylidenemalonaldehyde (IV) were prepared by condensation of bis(dimethylamino)trimethinium perchlorate with two vinylogues of benzaldehyde and a series of heterocyclic aldehydes. The reaction intermediate was isolated and shown by 1H NMR spectroscopy to be the bis-iminium salt III. The conformation of 3-phenylprop-2-enylidenemalonaldehyde (IVa), determined by its 1H NMR spectrum, may serve as a more general model of arylmethylenemalonaldehydes.

The acid-catalyzed rearrangement of methyl 3,4-O-benzylidene-β-D-ribopyranoside

1977 ◽  
Vol 55 (23) ◽  
pp. 4071-4077 ◽  
Author(s):  
David M. Clode
Keyword(s):  
Acid Concentration ◽  
Equilibrium Mixture ◽  
Nmr Spectrum ◽  
Ring Contraction ◽  
Acidic Conditions ◽  
Acid Catalyzed ◽  
Sole Product

Methyl 3,4-O-(R)-benzylidene-β-D-ribopyranoside (2) rapidly rearranged, under anhydrous acidic conditions, to give methyl 2,3-O-(R)-benzylidene-β-D-ribopyranoside (6). Further rearrangement of 2 and 6 gave the (S)-isomers 4 and 8, an equilibrium mixture of the four pyranoside acetals 2, 4, 6, and 8 resulting. At higher acid concentrations, the rearrangement proceeded, with ring contraction, to give the diastereomeric forms of methyl 2,3-O-benzylidene-β-D-ribofuranoside (11 and 13) as the sole product. Treatment of methyl 3,4-O-(S′)-benzylidene-β-D-ribopyranoside (4) with acid resulted in the immediate formation of the equilibrium mixture of pyranoside acetals. On increasing the acid concentration this mixture again underwent ring contraction to give the diastereomers 11 and 13 as the final product. The rearrangement of 2 and 4 was monitored by following the change in signals in the benzyl proton region of the nmr spectrum.

21,22-Disubstituted 18α,19βH-Ursane Derivatives with Oxabicyclooctane System in Ring E

1993 ◽  
Vol 58 (1) ◽  
pp. 173-190 ◽  
Author(s):  
Eva Klinotová ◽  
Jiří Klinot ◽  
Václav Křeček ◽  
Miloš Buděšínský ◽  
Bohumil Máca
Keyword(s):  
Spectral Data ◽  
Spin Systems ◽  
Coupling Constants ◽  
Complete Analysis ◽  
Nmr Spectrum ◽  
Proton Proton ◽  
H Nmr ◽  
Proton Coupling ◽  
C Nmr

Reaction of 3β-acetoxy-21,22-dioxo-18α,19βH-ursan-28,20β-olide (IIIa) and 20β,28-epoxy-21,22-dioxo-19α,19βH-ursan-3β-yl acetate (IIIb) with diazomethane afforded derivatives XII-XIV with spiroepoxide group in position 21 or 22, which were further converted into hydroxy derivatives XV and XVII. Ethylene ketals VIII-X were also prepared. In connection with the determination of position and configuration of the functional groups at C(21) and C(22), the 1H and 13C NMR spectral data of the prepared compounds are discussed. Complete analysis of two four-spin systems in the 1H NMR spectrum of bisethylenedioxy derivative Xb led to the proton-proton coupling constants from which the structure with two 1,4-dioxane rings condensed with ring E, and their conformation, was derived.

scholarly journals Structural studies of phosphorylation-dependent interactions between the V2R receptor and arrestin-2

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Qing-Tao He ◽  
Peng Xiao ◽  
Shen-Ming Huang ◽  
Ying-Li Jia ◽  
Zhong-Liang Zhu ◽  
...  
Keyword(s):  
Crystal Structures ◽  
Conformational Changes ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Interaction Sites ◽  
Receptor Interactions ◽  
Remote Sites ◽  
Genetic Code Expansion ◽  
G Protein Coupled ◽  
Interaction Change

AbstractArrestins recognize different receptor phosphorylation patterns and convert this information to selective arrestin functions to expand the functional diversity of the G protein-coupled receptor (GPCR) superfamilies. However, the principles governing arrestin-phospho-receptor interactions, as well as the contribution of each single phospho-interaction to selective arrestin structural and functional states, are undefined. Here, we determined the crystal structures of arrestin2 in complex with four different phosphopeptides derived from the vasopressin receptor-2 (V2R) C-tail. A comparison of these four crystal structures with previously solved Arrestin2 structures demonstrated that a single phospho-interaction change results in measurable conformational changes at remote sites in the complex. This conformational bias introduced by specific phosphorylation patterns was further inspected by FRET and 1H NMR spectrum analysis facilitated via genetic code expansion. Moreover, an interdependent phospho-binding mechanism of phospho-receptor-arrestin interactions between different phospho-interaction sites was unexpectedly revealed. Taken together, our results provide evidence showing that phospho-interaction changes at different arrestin sites can elicit changes in affinity and structural states at remote sites, which correlate with selective arrestin functions.

The solution conformation of prostacyclin as determined by high field proton magnetic resonance techniques

1980 ◽  
Vol 58 (10) ◽  
pp. 974-983 ◽  
Author(s):  
George Kotovych ◽  
Gerdy H. M. Aarts ◽  
Tom T. Nakashima ◽  
Glen Bigam
Keyword(s):  
Magnetic Resonance ◽  
Correlation Time ◽  
Proton Magnetic Resonance ◽  
Double Resonance ◽  
Relaxation Times ◽  
Segmental Motion ◽  
Solution Conformation ◽  
Nmr Spectrum ◽  
H Nmr ◽  
The Difference

The proton magnetic resonance (1H nmr) spectrum at 400 MHz of prostacyclin at pH 10.4 in glycine buffer has been completely analyzed utilizing homonuclear double resonance, inversion recovery, and difference nOe experiments. The spectral analysis shows that the two protons at C-4 are non-equivalent even though they are removed from the asymmetric centres at C-8 and C-9 by five bonds. The difference nOe measurements verify the configuration at C-5.Proton longitudinal relaxation times (T1) were measured at 400 and 200 MHz. From the T1 frequency dependence, effective rotational correlation times ranging from 2.3 × 10−10 to 3.0 × 10−10 s were calculated for H-5, H-9, H-11, and H-15. This indicates that the portion of the molecule encompassed by these protons has a longer correlation time than is observed for the C-2 and the C-17 to C-19 protons, for which the average correlation time is 1.2 × 10−10 s. Hence the aliphatic side chains have more segmental motion.

High field 1H NMR Studies of Sol-Gel Kinetics

1986 ◽  
Vol 73 ◽  
Author(s):  
Bruce D. Kay ◽  
Roger A. Assink
Keyword(s):  
Equilibrium Distribution ◽  
Sol Gel ◽  
Nmr Studies ◽  
H Nmr ◽  
Rate Limiting Step ◽  
Rate Of Hydrolysis ◽  
Acid Catalyzed ◽  
Product Species ◽  
Rate Limiting ◽  
Kinetics Of

ABSTRACTHigh resolution 1H NMR spectroscopy at high magnetic fields is employed to study the reaction kinetics of the Si(OCH3)4:CH3OH:H2O sol-gel system. Both the overall extent of reaction as a function of time and the equilibrium distribution of species are measured. In acid catalyzed solution, condensation is the rate limiting step while in base catalyzed solution, hydrolysis becomes rate limiting. A kinetic model in which the rate of hydrolysis is assumed to be independent of the adjacent functional groups is presented. This model correctly predicts the distribution of product species during the initial stages of the sol-gel reaction.

scholarly journals Synthesis, Characterization, and Biological Studies of a Piperidinyl Appended Dipicolylamine Ligand and Its Rhenium Tricarbonyl Complex as Potential Therapeutic Agents for Human Breast Cancer

2016 ◽  
Vol 2016 ◽  
pp. 1-10 ◽  
Author(s):  
Amali Subasinghe ◽  
Inoka C. Perera ◽  
Svetlana Pakhomova ◽  
Theshini Perera
Keyword(s):  
Breast Cancer ◽  
Anticancer Agents ◽  
Human Breast Cancer ◽  
Human Breast ◽  
Tricarbonyl Complex ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Biological Studies ◽  
Visible Spectra ◽  
Uv Visible

A novel ligand bearing a central piperidinyl sulfonamide group, N(SO2pip)dpa, and its corresponding Re tricarbonyl complex, [Re(CO)3(N(SO2pip)dpa)]+, have been synthesized in good yield. The methylene CH2signal seen as a singlet (4.54 ppm) in a1H NMR spectrum of the ligand in DMSO-d6appears as two doublets (5.39, 5.01 ppm) in a spectrum of the [Re(CO)3(N(SO2pip)dpa)]+complex and confirms the presence of magnetically nonequivalent protons upon coordination to Re. Structural results revealed that the Re–N bond lengths fall within the normal range establishing coordination of ligand to metal. The presence of intraligandπ→π⁎andn→π⁎transitions is indicated by the absorption peaks around 200–250 nm in UV-visible spectra. Absorption peaks in UV-visible spectra around 300 nm for metal complexes were identified as MLCT transitions. The S–N stretch observed as a strong peak at 923 cm−1for N(SO2pip)dpa appeared at a shorter frequency, at 830 cm−1in an FTIR spectrum of the [Re(CO)3(N(SO2pip)dpa)]+. The intense fluorescence displayed by the N(SO2pip)dpa ligand has quenched upon coordination to Re. Relatively low IC50values given by human breast cancer cells, MCF-7, (N(SO2pip)dpa = 139 μM, [Re(CO)3(N(SO2pip)dpa)]+= 360 μM) indicate that N(SO2pip)dpa and [Re(CO)3(N(SO2pip)dpa)]+are promising novel compounds that can be further investigated on their usage as potential anticancer agents.

Organometallic oxides: preparation of the cluster [(η-C5Me5)Mo]4O7 by reduction of [(η-C5Me5)MoCl(O)]2(μ-O) or (η-C5Me5)MoCl2(O)

2000 ◽  
Vol 78 (3) ◽  
pp. 383-394
Author(s):  
Frank Bottomley ◽  
Victor Sanchez ◽  
Robert C Thompson ◽  
Olusola O Womiloju ◽  
Zhiqiang Xu
Keyword(s):  
Nmr Spectra ◽  
Chloroform Solution ◽  
X Ray Diffraction ◽  
Broad Resonance ◽  
Nmr Spectrum ◽  
X Ray ◽  
Temperature Range ◽  
H Nmr ◽  
Tributyltin Hydride ◽  
Effective Moment

Reduction of [(η-C5Me5)MoCl(O)]2(μ-O) or (η-C5Me5)MoCl2(O) with sodium or magnesium amalgam, magnesium turnings, or tributyltin hydride produced [(η-C5Me5)Mo]4O7, with [(η-C5Me5)Mo(O)(μ-O)]2 as a co-product. [(η-C5Me5)Mo]4O7 was characterized by X-ray diffraction, mass spectrometry, 1H NMR and IR spectroscopies, and magnetism. Crystals of [(η-C5Me5)Mo]4O7 contained a tetrahedral [(η-C5Me5)Mo]4 unit (Mo-Mo = 2.909 (3) Å) with the Mo4O7 core having the structure Mo4(μ2-O(b))3(µ2-O(c))3(µ3-O(a)) (3). Microcrystalline samples of [(η-C5Me5)Mo]4O7 were paramagnetic over the temperature range 2-300 K, with an effective moment of 1.26 μB at 300 K. [(η-C5Me5)Mo]4O7 was also paramagnetic in chloroform solution, over the temperature range 223-298 K, with an effective moment of 1.43 µB at 298 K. The 1H NMR spectrum showed a broad resonance at 16.3 ppm (Δν 1/2 = 113 Hz) and two narrow resonances at 1.89 ppm and 1.69 ppm (Δν 1/2 = 5 Hz). The magnetism and NMR spectra showed that [(η-C5Me5)Mo]4O7 existed in two forms which were in equilibrium in solution. One form was paramagnetic (S = 1), with the Mo4O7 core having the geometry 3, and the other was diamagnetic (S = 0), with the Mo4O7 core having the geometry 4.Key words: cluster, cyclopentadienyl, molybdenum, oxide, paramagnetism.

scholarly journals Beiträge zur Chemie des Phosphors, 204. Zur Existenz eines Triphosphacyclobutenid-Ions P3CH2Ɵ / Contributions to the Chemistry of Phosphorus, 204. On the Existence of a Triphosphacyclobutenide Ion P3CH2e

1990 ◽  
Vol 45 (8) ◽  
pp. 1139-1142 ◽  
Author(s):  
Marianne Baudler ◽  
Josef Hahn
Keyword(s):  
White Phosphorus ◽  
Complete Analysis ◽  
Nmr Spectrum ◽  
H Nmr ◽  
Low Field

The structure of the reaction product of white phosphorus and sodium in diglyme which exhibits a low field AB2 system in the 31P{1H} NMR spectrum [4] has been reexamined. According to the results of a complete analysis of its proton coupled 31P NMR spectrum (ABB′XX′ system), the compound is the hitherto unknown 1,2,3-triphosphacyclopentadienide ion P3(CH)2⊖ (4), and not the triphosphacyclobutenide ion P3CH2⊖(3) previously assumed [4]. The parameters of the Ρ,Η-coupled 31P NMR spectrum of the tetraphosphacyclopentadienide ion P4CH⊖ (2) have also been calculated.

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