Alkaloids of the Australian Rutaceae: Melicope fareana. V. The Structure of the Alkaloids

1949 ◽  
Vol 2 (2) ◽  
pp. 282 ◽  
Author(s):  
WD Crow ◽  
JR Price
Keyword(s):  
Hydrogen Bonding ◽  
Oxygen Atom ◽  
Nitrous Acid ◽  
Degradation Products ◽  
Structural Formula ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Complete Structure ◽  
Methylenedioxy Group ◽  
Alternative Structures

Melicopine, melicopidine, and melicopicine are shown to be members of a new group of alkaloids derived from acridine. The structure of melicopicine, 1,2,3,4-tetramethoxy-10-methylacridone (II), is deduced from data reported in earlier papers. The presence of the same 10-methylacridone skeleton in melicopidine and melicopine is established by conversion of the trimethoxyphenols obtained from them by fission of the methylenedioxy ring with methanolic potash to the respective dimethoxy-o- and p-quinones previously prepared from melicopicine. This conversion also establishes the position of the methylenedioxy group in melicopine relative to the hydroxyl group in normelicopicine. Similar considerations applied to the ethoxydimethoxyphenols show the position of the methylenedioxy group in melicopidine relative to the hydroxyl group in normelicopicine, and in this case, lead to the complete structure for the alkaloid (XIII). The action of nitrous acid on normelicopine and normelicopidine gives two hydroxymethoxyquinones isomeric with that obtained by the action of sodium carbonate on the dimethoxy-o- and p-quinones. The same two hydroxymethoxyquinones also result from the action of caustic soda on the dimethoxy-o- and p-quinones respectively. Their structures, which can be deduced from the second method of preparation, confirm the positions of the methylenedioxy group in melicopine and melicopidine relative to the hydroxyl group of normelicopicine, and prove that the hydroxyl groups in normelicopine and normelicopidine are in the same position as that in normelicopicine, but they do not make possible a choice between alternative structures for melicopine. This choice depends on the position of the hydroxyl group of the noralkaloids relative to the remainder of the acridone molecule. By consideration of the mechanism of fission of the methylenedioxy ring, the hydroxyl group of the noralkaloids is shown to be situated peri to the acridone oxygen atom, i.e. at position 4. This is confirmed by the occurrence of hydrogen bonding. Consequently the complete structural formula for melicopine is XXIII. The properties of the alkaloids and a number of the degradation products are discussed.

scholarly journals Summation Solute Hydrogen Bonding Acidity Values for Hydroxyl Substituted Flavones Determined by NMR Spectroscopy

2013 ◽  
Vol 8 (1) ◽  
pp. 1934578X1300800 ◽  
Author(s):  
William L. Whaley ◽  
Ekua M. Okoso-amaa ◽  
Cody L. Womack ◽  
Anna Vladimirova ◽  
Laura B. Rogers ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Nmr Spectroscopy ◽  
Intramolecular Interactions ◽  
Hydroxyl Group ◽  
Accurate Estimation ◽  
Hydroxyl Groups ◽  
Linear Free Energy Relationship ◽  
Hydrogen Bond Donor ◽  
Linear Free Energy ◽  
Drug Molecules

The flavonoids are a structurally diverse class of natural products that exhibit a broad spectrum of biochemical activities. The flavones are one of the most studied flavonoid subclasses due to their presence in dietary plants and their potential to protect human cells from reactive oxygen species (ROS). Several flavone compounds also mediate beneficial actions by direct binding to protein receptors and regulatory enzymes. There is current interest in using Quantitative Structure Activity Relationships (QSARs) to guide drug development based on flavone lead structures. This approach is most informative when it involves the use of accurate physical descriptors. The Abraham summation solute hydrogen bonding acidity ( A) is a descriptor in the general solvation equation. It defines the tendency of a molecule to act as a hydrogen bond donor, or acid, when surrounded by solvent molecules that are hydrogen bonding acceptors, or bases. As a linear free energy relationship, it is useful for predicting the absorption and uptake of drug molecules. A previously published method, involving nuclear magnetic resonance (NMR) spectroscopy, was used to evaluate A for the monohydroxyflavones (MHFs). Values of A ranged from 0.02, for 5-hydroxyflavone, to 0.69 for 4′-hydroxyflavone. The ability to examine separate NMR signals for individual hydroxyl groups allowed the investigation of intramolecular interactions between functional groups. The value of A for the position 7 hydroxyl group of 7-hydroxyflavone was 0.67. The addition of a position 5 hydroxyl group (in 5,7-dihydroxyflavone) increased the value of A for the position 7 hydroxyl group to 0.76. Values of A for MHFs were also calculated by the program ACD-Absolve and these agreed well with values measured by NMR. These results should facilitate more accurate estimation of the values of A for structurally complex flavones with pharmacological activities.

The proton affinities and deprotonation enthalpies of β-D-fructopyranose and α-L-sorbopyranose

1991 ◽  
Vol 69 (12) ◽  
pp. 1917-1928 ◽  
Author(s):  
Robert J. Woods ◽  
Walter A. Szarek ◽  
Vedene H. Smith Jr.
Keyword(s):  
Hydrogen Bonding ◽  
Oxygen Atom ◽  
Intramolecular Hydrogen Bonding ◽  
Hydroxyl Group ◽  
Proton Affinities ◽  
Naturally Occurring ◽  
Acid Catalyzed ◽  
Acids And Bases ◽  
Intramolecular Hydrogen ◽  
Hydrolysis Of

The proton affinities (PAs) and deprotonation enthalpies (DPEs) were calculated for the pyranoid forms of two naturally occurring sugars, D-fructose and L-sorbose. In both molecules the PAs of the primary hydroxyl group (HO-1), the anomeric hydroxyl group (HO-2), and the ring-oxygen atom (O-6) were calculated, as were the DPEs of HO-1 and HO-2. The stabilities of the conjugate acids and bases of these sugars are enhanced by the presence of intramolecular hydrogen bonding, a feature that is significant in explaining the differences in sweetness and the rates of mutarotation of the title compounds, as well as the differences in the rates of acid-catalyzed hydrolysis of ketopyranosides. Key words: proton affinity, deprotonation enthalpy, ab initio calculations, AM1, hexuloses.

The Dielectic properties of Crystalline Alcohols containing sterically hindered Hydroxyl groups

1953 ◽  
Vol 6 (2) ◽  
pp. 104 ◽  
Author(s):  
RJ Meakins
Keyword(s):  
Hydrogen Bonding ◽  
Hydroxyl Group ◽  
Appreciable Amount ◽  
Hydroxyl Groups ◽  
Dipole Orientation ◽  
Hindered Rotation ◽  
Dielectric Absorption ◽  
Free Hydroxyl ◽  
Sterically Hindered ◽  
High Dielectric

It has been previously suggested that the high dielectric absorption of certain crystalline forms of long-chain alcohols is associated with hydrogen-bonding of the hydroxyl groups. This theory is supported by the results given in the present paper, which show that with other alcohols, in which the hydroxyl groups are sterically hindered, the loss is almost completely eliminated. The smallest losses are obtained with triphenylcarbinol and cholesterol which both possess hydroxyl groups embedded in a bulky molecular structure. For the former compound, infra-red data from the literature indicate the absence of any appreciable amount of hydrogen-bonding and are thus in agreement with the evidence from dielectric measurements. High frequency absorption observed in these compounds is considered to be associated with dipole orientation resulting from hindered rotation of the free hydroxyl groups. The effects of steric hindrance of the hydroxyl group are also observed in tert.-butanol.

scholarly journals Structural requirements for active intestinal transport. The nature of the carrier–sugar bonding at C-2 and the ring oxygen of the sugar

1970 ◽  
Vol 118 (5) ◽  
pp. 843-850 ◽  
Author(s):  
J. E. G. Barnett ◽  
A. Ralph ◽  
K. A. Munday
Keyword(s):  
Oxygen Atom ◽  
Intestinal Transport ◽  
Competitive Inhibitor ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Sulphur Atom ◽  
Intestinal Tissue ◽  
Structural Requirements ◽  
Galactose Transport ◽  
Steric Constraints

Several weakly transported sugars were tested for transport by the Na+-dependent sugar carrier with slices of everted hamster intestinal tissue. Sugars were assumed to be transported by this carrier if the accumulation was diminished in the absence of Na+ and in the presence of the competitive inhibitor 1,5-anhydro-d-glucitol. The extent of accumulation was correlated with the number of hydroxyl groups in the d-gluco configuration if the ring oxygen was placed in the normal d-glucose position. 5-Thio-d-glucose, with a sulphur atom in the ring, was transported at about the same rate as d-glucose and had a similar Ki for d-galactose transport, but myoinositol was poorly accumulated. It is suggested that there is no hydrogen bonding at the ring oxygen atom, but that the oxygen atom is found at this position as a result of steric constraints. No sugar without a hydroxyl group in the d-gluco position at C-2 of the sugar, including d-mannose, 2-deoxy-d-glucose, 2-chloro-2-deoxy-d-glucose and 2-deoxy-2-fluoro-d-glucose, was transported by the Na+-dependent carrier, but these sugars and l-fucose weakly and competitively inhibit the Na+-dependent accumulation of l-glucose into slices of everted hamster intestinal tissue. It is concluded that the bond between the carrier and C-2 of the sugar may be covalent, and a possible mechanism for active intestinal transport is proposed.

Conformation of the esters of steroid hydroxyl groups by infrared spectroscopy

1969 ◽  
Vol 47 (9) ◽  
pp. 1601-1603 ◽  
Author(s):  
C. R. Narayanan ◽  
M. R. Sarma ◽  
T. K. K. Srinivasan ◽  
M. S. Wadia
Keyword(s):  
Hydrogen Bonding ◽  
Infrared Spectroscopy ◽  
Carbonyl Group ◽  
Hydroxyl Group ◽  
Spectral Studies ◽  
Hydroxyl Groups ◽  
Hydrogen Atoms ◽  
Infrared Spectral

Infrared spectral studies show that the carbonyl group of the esters of steroid hydroxyl groups are stabilized near the adjacent alkyl hydrogen atoms; this energy of stabilization appears to be more than that of hydrogen bonding between the carbonyl and a nearby hydroxyl group.

Crystal structure of i -erythritol and its relationship to some derived d and l and racemic substances

1959 ◽  
Vol 250 (1262) ◽  
pp. 301-315 ◽  
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Three Dimensional ◽  
Tetragonal Structure ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Main Structure ◽  
Hydrogen Bonded

Meso erythritol forms a tetragonal structure in which the molecules are centro-symmetric. Each α -hydroxyl group forms part of a tetragonal spiral of hydrogen bonds. These spirals alone are sufficient to link all the molecules of the crystal into a three-dimensional hydrogen-bonded complex. The β -hydroxyl groups of neighbouring molecules form closed circuits of four hydrogen bonds in a tetrahedron so flattened as to be almost a square. These closed circuits are also by themselves sufficient to link all molecules in the crystal into a three-dimensional complex. When some of the hydroxyl groups are replaced by fluorine atoms of approximately the same size, the main structure should be retained if sufficient hydrogen bonding is left. It is possible, therefore, to predict structures for meso , d , l and racemic forms of some of the fluoro-substituted derivatives. 2-deoxy-2-fluoro (±) erythritol has been examined and found to have the expected racemic structure. The possibility of forms transitional between dextro , racemic, and laevo , is discussed.

scholarly journals Influence of Multiple & Cooperative Hydrogen Bonding on the Acidity of Polyhydroxylated Piperidines: Electron Density Topological Analysis

2021 ◽  
Author(s):  
Marjan Jebeli Javan
Keyword(s):  
Hydrogen Bonding ◽  
Hydrogen Bonds ◽  
Gas Phase ◽  
Topological Analysis ◽  
Three Dimensional ◽  
Solution Phase ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Gas Phase Acidity ◽  
Polarized Continuum Model

Abstract Hydrogen bonds are the presiding concepts for arranging the three-dimensional forms of biological molecules like proteins, carbohydrates and nucleic acids, and acts as guides for proton transfer reactions. Gas-phase acidity and pKa calculations in dimethyl sulfoxide on a line of polyhydroxylated piperidines specify that multiple hydrogen bonds lead to enhance acidities.The gas-phase acidity (GPA) of polyhydroxylated piperidines was investigated by MP2/6-311++G(d,p)//B3LYP/6-311++G(d,p) method. For each structure, varied primary and secondary hydroxyl groups were deprotonated. The natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) analyses have also been used to realize the character of the hydrogen bonding interactions in these compounds. The results show by adding each hydroxyl group, ΔHacid in the gas phase (it becomes less endothermic) and pKa value in the solution phase was decreased. Therefore, intramolecular hydrogen bonds lead to enhance the acid strength. In both the gas phase and solution phase, the β-Nojrimycin-OH2 (β-1-OH2) was found to be the most acidic compound with calculated gas-phase acidity (GPA) of 349.4 kcal.mol-1 and the pKa value of 22.0 (8.0 pKa units more acidic than 1-propanol).It was also shown, applying the polarized continuum model (PCM), there is a superior linear correlation with the gas phase acidities (GPAs) of polyhydroxylated piperidines and their calculated pKa (DMSO) values.

Jahn-Teller Effect in Hexahydroxocuprate(II) Complexes

1995 ◽  
Vol 60 (9) ◽  
pp. 1429-1434
Author(s):  
Martin Breza
Keyword(s):  
Hydrogen Bonding ◽  
Quantum Chemical ◽  
Potential Surface ◽  
Hydroxyl Group ◽  
Chemical Calculation ◽  
Teller Distortion ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Extremal Values ◽  
Jahn Teller Distortion

Using semiempirical CNDO-UHF method the adiabatic potential surface of 2[Cu(OH)6]4- complexes is investigated. The values of vibration and vibronic constants for Eg - (a1g + eg) vibronic interaction attain extremal values for the optimal O-H distance. The Jahn-Teller distortion decreases with increasing O-H distance. The discrepancy between experimentally observed elongated bipyramid of [Cu(OH)6]4- in Ba2[Cu(OH)6] and the compressed one obtained by quantum-chemical calculation is explainable by hydrogen bonding of the axial hydroxyl group.

scholarly journals Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Molecules ◽  
2021 ◽  
Vol 26 (8) ◽  
pp. 2131
Author(s):  
Leonardo Dalseno Antonino ◽  
Júlia Rocha Gouveia ◽  
Rogério Ramos de Sousa Júnior ◽  
Guilherme Elias Saltarelli Garcia ◽  
Luara Carneiro Gobbo ◽  
...  
Keyword(s):  
Experimental Work ◽  
Chemical Structure ◽  
31P Nmr ◽  
Kraft Lignin ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Diphenylmethane Diisocyanate ◽  
Complex Chemical ◽  
Heterogeneous Reactivity ◽  
Phenolic Hydroxyl Groups

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. 31P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.

scholarly journals Enhancement of Antioxidant and Hydrophobic Properties of Alginate via Aromatic Derivatization: Preparation, Characterization, and Evaluation

Polymers ◽  
2021 ◽  
Vol 13 (15) ◽  
pp. 2575
Author(s):  
Smaher M. Elbayomi ◽  
Haili Wang ◽  
Tamer M. Tamer ◽  
Yezi You
Keyword(s):  
Radical Scavenging Activity ◽  
Radical Scavenging ◽  
Hydroxyl Group ◽  
Hydroxyl Groups ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Benzoyl Group ◽  
Antioxidant Evaluation ◽  
Thermo Stability

The preparation of bioactive polymeric molecules requires the attention of scientists as it has a potential function in biomedical applications. In the current study, functional substitution of alginate with a benzoyl group was prepared via coupling its hydroxyl group with benzoyl chloride. Fourier transform infrared spectroscopy indicated the characteristic peaks of aromatic C=C in alginate derivative at 1431 cm−1. HNMR analysis demonstrated the aromatic protons at 7.5 ppm assigned to benzoyl groups attached to alginate hydroxyl groups. Wetting analysis showed a decrease in hydrophilicity in the new alginate derivative. Differential scanning calorimetry and thermal gravimetric analysis showed that the designed aromatic alginate derivative demonstrated higher thermo-stability than alginates. The aromatic alginate derivative displayed high anti-inflammatory properties compared to alginate. Finally, the in vitro antioxidant evaluation of the aromatic alginate derivative showed a significant increase in free radical scavenging activity compared to neat alginate against DPPH (2,2-diphenyll-picrylhydrazyl) and ABTS free radicals. The obtained results proposed that the new alginate derivative could be employed for gene and drug delivery applications.

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