Search results for "Intramolecular force"
showing 10 items of 599 documents
ChemInform Abstract: Synthetic Approaches to Antiinflammatory Macrolactones of the Oxacyclododecindione Type.
2015
A variety of attempts to synthesize oxacyclododecindione macrolactones through carbonylative ring-closure, intramolecular alkyne hydroacyalation, and Ru-catalyzed double bond isomerization fails.
Approaching an experimental electron density model of the biologically active trans ‐epoxysuccinyl amide group—Substituent effects vs. crystal packing
2017
The trans-epoxysuccinyl amide group as a biologically active moiety in cysteine protease inhibitors such as loxistatin acid E64c has been used as a benchmark system for theoretical studies of environmental effects on the electron density of small active ingredients in relation to their biological activity. Here, the synthesis and the electronic properties of the smallest possible active site model compound are reported to close the gap between the unknown experimental electron density of trans-epoxysuccinyl amides and the well-known function of related drugs. Intramolecular substituent effects are separated from intermolecular crystal packing effects on the electron density, which allows us…
Light induced processes in thin films of indandione type organic molecules
2007
The optically induced switching of material properties is important for investigations of opto-electronic effects and optomechanical properties. Investigated organic materials contain chromophore dipole consisting of acceptor and donor groups bridged by a delocalized p-electron system. Both calculations and experimental data show a reversible highly dipolar photoinduced intra molecular charge transfer in indandione type molecules (DMABI) accompanied by change of the sign and the value of the dipole moment. Investigations of optical properties of thin host-guest polymer films show that the photoinduced process of DMABI is related to the photoinduced switching between two equally stable state…
On the relations between aromaticity and substituent effect
2019
Aromaticity/aromatic and substituent/substituent effects belong to the most commonly used terms in organic chemistry and related fields. The quantitative description of aromaticity is based on energetic, geometric (e.g., HOMA), magnetic (e.g., NICS) and reactivity criteria, as well as the properties of the electronic structure (e.g., FLU). The substituent effect can be described using either traditional Hammett-type substituent constants or characteristics based on quantum-chemistry. For this purpose, the energies of properly designed homodesmotic reactions and electron density distribution are used. In the first case, a descriptor named SESE (energy stabilizing the substituent effect) is o…
17O NMR study of isomeric monochloro- and monohydroxy-benzaldehydes and chlorinated salicylaldehydes
1991
The 17O NMR chemical shifts of isomeric monochloro- and monohydroxy-benzaldehydes and chlorinated salicylaldehydes were measured at 40°C for 0.25 M CDCI3 solutions. The 17O NMR chemical shift of the carbonyl oxygen of the compounds studied varies from 506 to 573 ppm measured from external D2O. The observed variation is probably mainly due to the intramolecular hydrogen bonding between the adjacent carbonyl and hydroxyl groups. The 17O NMR chemical shift range of the hydroxyl oxygen is from 80 to 98 ppm.
Calix[4]arenes with resorcinol units incorporated in 2,6-position
1990
Abstract Calix[4]arenes containing one or two resorcinol units incorporated via their 2,6-positions were prepared by fragment condensation. Due to the cyclic array of intramolecular hydrogen bonds these molecules assume the cone-conformation.
“Tail–Tail Dimerization” of Ferrocene Amino Acid Derivatives
2010
Acid anhydrides of N-protected 1'-aminoferrocene-1-carboxylic acid (Fca) have been prepared and spectroscopically characterized (protection group Boc, Fmoc, Ac; 4a―4c). The structure of the Boc-derivative 4a has been determined by single-crystal X-ray crystallography. An intramolecular N― H···O hydrogen bond involving the carbamate units results in a ring structure containing the two ferrocene units, the anhydride moiety, and the hydrogen bond. In the crystal, the individual molecules are connected by intermolecular N-H···O hydrogen bonds of the carbamate unit. Experimental and theoretical studies suggest that the ring motif is also a dominant species in solution. Electronic communication a…
Diferrocenyl tosyl hydrazone with an ultrastrong NHFe hydrogen bond as double click switch.
2014
The intramolecular NH⋯Fe hydrogen bond in diferrocenyl hydrazone 2 raises the barrier for intramolecular electron transfer in its mixed-valent cation 2+ and is only disrupted by double oxidation to 22+.
1H-nmr studies of polyoxyethylene-bound homo-oligo-L-methionines
1982
The use of 1H-nmr spectroscopy is demonstrated to be a useful analytical method to characterize the structure of synthetic peptides attached to soluble, macromolecular polyoxyethylene (POE) supports in the liquid-phase method (LPM) of peptide synthesis. We report an extensive 360-MHz 1H-nmr study of POE-bound homo-oligo-L-methionine peptides. A combination of high field and selective saturation or Redfield pulse methods allows resolution of individual backbone NH and α-CH resonances of dilute peptides in the presence of strong resonances from macromolecular POE and/or protonated solvents. The nmr spectra for the POE-bound peptides in CDCl3 are qualitatively similar to those of the low-molec…
An Efficient and Simple Entry to N-Substituted beta-Enamino Acid Derivatives from 2-Alkyl-2-oxazolines and 2-Alkyl-2-thiazolines.
1996
Reaction of azaenolates of 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds 1-2 generally appear in one tautomeric form, imino or enamino, depending on the nature of the imidoyl chloride. The configuration of the enamino moiety (Z) and the conformation (s-cis) of compounds 1-2 obtained were established by an NMR study and unequivocally set by nuclear Overhauser effect difference experiments. An X-ray structure of compound 1e is also reported, showing a strong intramolecular NH.N hydrogen bond. Ab initio calculations (HF/3-21G and HF/…