Effects of benzoyl group substituents on the mesomorphic properties of 5-alkoxy-2-benzoylaminotropones

Three types of 5-alkoxy-2-benzoylaminotropones, containing an electron-donating group and seven types of derivatives with electron-withdrawing groups on the benzoyl group, were prepared in order to study the thermal ranges of the mesophases exhibited. The troponoid amides had higher transition temperatures than the corresponding troponoid esters and benzenoid amides. From the ¹H NMR spectroscopic measurements and X-ray crystallographic analysis of 5-butoxy-2-(4-methoxybenzoylamino)tropone, it was observed that the benzoyl carbonyl group faced to the H-3 of the tropone ring to form an intramolecular hydrogen bond between the tropone carbonyl and the amide NH groups. The intramolecular hydrogen bonding of the troponoid amides made the molecules flat, inducing strong π–π intermolecular interactions between head-to-tail dimers and so reduced the possibility of intermolecular hydrogen bonding between the NH group and the carbonyl group of neighbouring molecules so decreasing melting points. Electron-donating groups enhanced the appearance of nematic phases while electron-withdrawing groups promoted smectic A phases.     

Effects of benzoyl group substituents on the mesomorphic properties of 5-alkoxy-2-benzoylaminotropones

Three types of 5-alkoxy-2-benzoylaminotropones, containing an electron-donating group and seven types of derivatives with electron-withdrawing groups on the benzoyl group, were prepared in order to study the thermal ranges of the mesophases exhibited. The troponoid amides had higher transition temperatures than the corresponding troponoid esters and benzenoid amides. From the ¹H NMR spectroscopic measurements and X-ray crystallographic analysis of 5-butoxy-2-(4-methoxybenzoylamino)tropone, it was observed that the benzoyl carbonyl group faced to the H-3 of the tropone ring to form an intramolecular hydrogen bond between the tropone carbonyl and the amide NH groups. The intramolecular hydrogen bonding of the troponoid amides made the molecules flat, inducing strong π-π intermolecular interactions between head-to-tail dimers and so reduced the possibility of intermolecular hydrogen bonding between the NH group and the carbonyl group of neighbouring molecules so decreasing melting points. Electron-donating groups enhanced the appearance of nematic phases while electron-withdrawing groups promoted smectic A phases.     

Roles of sigmatropic migration of a benzoyl group and intermolecular hydrogen bonding between a tropone carbonyl and an NH group on the mesomorphic properties of 2-(4-alkoxybenzoyloxy)-5-alkylaminotropones and 5-alkoxy-2-(4-alkylaminobenzoyloxy)tropo

The mesomorphic properties of 2-(4-alkoxybenzoyloxy)-5-alkylaminotropones and 5-alkoxy-2-(4-alkylaminobenzoyloxy)tropones are discussed on the basis of results obtained by X-ray crystallographic and X-ray diffraction studies, as well as temperature-dependent FTIR spectral measurements. The X-ray crystallographic analysis of 2-(4-dodecylaminobenzoyloxy)-5-tetradecyloxytropone (2f) indicated that it formed a head-to-tail dimer through an intermolecular hydrogen bond between the NH and the tropone carbonyl group. The X-ray diffraction study of compound 2f suggested that the molecules formed interdigitated bilayer smectic C phases with a tilt angle of as much as c. 40° to a layer plane. The corresponding benzenoids, however, were non-mesomorphic, with higher melting points than the troponoids. In the troponoids, sigmatropic migration of the benzoyl group weakened the intermolecular hydrogen bonding and assisted the occurrence of mesomorphic properties.     

Dimeric liquid crystals with two troponoid mesogenic moieties: effect of the direction of the carbonyl group on the mesomorphic properties

Three twin types of troponoid liquid crystals, in which the directions of the tropone carbonyl groups are different from each other, were prepared to establish their thermal properties. Symmetrical type I dimers, in which the two tropone carbonyl groups are directed inwards, had monotropic smectic C phases, whereas two other symmetrical type IIa and IIb dimers, whose troponoid dipoles are directed outwards, were not mesomorphic except for one type IIa compound having two long terminal chains and a short alkylene spacer. Unsymmetrical type III dimers had smectic A phases. Among the dimers, unsymmetrical type III dimers had the highest clearing point when the number of atoms of the inner and outer spacers was fixed. X-ray diffraction studies of a type III dimer, in which the number of the atoms of the inner spacer was odd, showed that the molecules form an interdigitated layer structure. The binary system between type I and type IIb dimers showed an induced enantiotropic smectic A phase, in which the dipole moments of the tropone rings were cancelled.     

Dimeric liquid crystals with two troponoid mesogenic moieties: effect of the direction of the carbonyl group on the mesomorphic properties

Three twin types of troponoid liquid crystals, in which the directions of the tropone carbonyl groups are different from each other, were prepared to establish their thermal properties. Symmetrical type I dimers, in which the two tropone carbonyl groups are directed inwards, had monotropic smectic C phases, whereas two other symmetrical type IIa and IIb dimers, whose troponoid dipoles are directed outwards, were not mesomorphic except for one type IIa compound having two long terminal chains and a short alkylene spacer. Unsymmetrical type III dimers had smectic A phases. Among the dimers, unsymmetrical type III dimers had the highest clearing point when the number of atoms of the inner and outer spacers was fixed. X-ray diffraction studies of a type III dimer, in which the number of the atoms of the inner spacer was odd, showed that the molecules form an interdigitated layer structure. The binary system between type I and type IIb dimers showed an induced enantiotropic smectic A phase, in which the dipole moments of the tropone rings were cancelled.     

Intermolecular hydrogen bonding as an aid to the preferential exhibition of the smectic C phase in troponoid liquid crystals

Abstract

2-(4-Alkoxybenzoyloxy)-5-alkylaminotropone and 5-alkoxy-2-(4-alkylaminobenzoyloxy)tropone liquid crystals showed the smectic C phase exclusively. Variable temperature FT-IR spectra indicated that intermolecular hydrogen bonding between the NH and tropone C=O groups assisted the appearance of the mesophase. 4-Alkoxyphenyl 4-alkylaminobenzoates were non-mesogenic.     

Roles of sigmatropic migration of a benzoyl group and intermolecular hydrogen bonding between a tropone carbonyl and an NH group on the mesomorphic properties of 2-(4-alkoxybenzoyloxy)-5-alkylaminotropones and 5-alkoxy-2-(4-alkylaminobenzoyloxy)tropo

The mesomorphic properties of 2-(4-alkoxybenzoyloxy)-5-alkylaminotropones and 5-alkoxy-2-(4-alkylaminobenzoyloxy)tropones are discussed on the basis of results obtained by X-ray crystallographic and X-ray diffraction studies, as well as temperature-dependent FTIR spectral measurements. The X-ray crystallographic analysis of 2-(4-dodecylaminobenzoyloxy)-5-tetradecyloxytropone (2f) indicated that it formed a head-to-tail dimer through an intermolecular hydrogen bond between the NH and the tropone carbonyl group. The X-ray diffraction study of compound 2f suggested that the molecules formed interdigitated bilayer smectic C phases with a tilt angle of as much as c. 40° to a layer plane. The corresponding benzenoids, however, were non-mesomorphic, with higher melting points than the troponoids. In the troponoids, sigmatropic migration of the benzoyl group weakened the intermolecular hydrogen bonding and assisted the occurrence of mesomorphic properties.     

Mesomorphic properties of 2-acyloxy5-(4-alkoxyphenylazo)tropones, 2-acyloxy-5-(4-alkylphenylazo)tropones,and 2-acyloxy-5-(4-alkoxycarbonylphenylazo)tropones

Three series of mesomorphic 2-acyloxy-5-phenylazotropones with alkoxy, alkyl, and alkoxycarbonyl groups at C-4 on the phenyl ring were prepared. It was known that the corresponding 5-phenylazotropolone derivatives and their methyl ethers were not mesomorphic. 2-Acetyl-5-(4-hexyloxyphenylazo)tropone, however, shows a monotropic smectic A phase. Even an acetyl group is therefore able to induce a mesophase. The effects of terminal substitution of the tropone ring by groups such as alkoxy, alkoxycarbonyl, and alkyl on the clearing points are discussed.     

Mesomorphic properties of 2-acyloxy5-(4-alkoxyphenylazo)tropones, 2-acyloxy-5-(4-alkylphenylazo)tropones, and 2-acyloxy-5-(4-alkoxycarbonylphenylazo)tropones

Three series of mesomorphic 2-acyloxy-5-phenylazotropones with alkoxy, alkyl, and alkoxycarbonyl groups at C-4 on the phenyl ring were prepared. It was known that the corresponding 5-phenylazotropolone derivatives and their methyl ethers were not mesomorphic. 2-Acetyl-5-(4-hexyloxyphenylazo)tropone, however, shows a monotropic smectic A phase. Even an acetyl group is therefore able to induce a mesophase. The effects of terminal substitution of the tropone ring by groups such as alkoxy, alkoxycarbonyl, and alkyl on the clearing points are discussed.     

Two polymorphs of N‐(2‐methoxyphenyl)‐4‐oxo‐4H‐chromone‐3‐carboxamide

The title compound, C₁₇H₁₃NO₄, crystallizes in two polymorphic forms, each with two molecules in the asymmetric unit and in the monoclinic space group P2₁/c. All of the molecules have intramolecular hydrogen bonds involving the amide group. The amide N atoms act as donors to the carbonyl group of the pyrone and also to the methoxy group of the benzene ring. The carbonyl O atom of the amide group acts as an acceptor of the β and β′ C atoms belonging to the aromatic rings. These intramolecular hydrogen bonds have a profound effect on the molecular conformation. In one polymorph, the molecules in the asymmetric unit are linked to form dimers by weak C—H...O interactions. In the other, the molecules in the asymmetric unit are linked by a single weak C—H...O hydrogen bond. Two of these units are linked to form centrosymmetric tetramers by a second weak C—H...O interaction. Further interactions of this type link the molecules into chains, so forming a three‐dimensional network. These interactions in both polymorphs are supplemented by π–π interactions between the chromone rings and between the chromone and methoxyphenyl rings.     

Amide hydrogen bonding: control of the molecular and extended structures of two symmetrical pyridine‐2‐carboxamide derivatives

The crystal structures of two symmetrical pyridine‐2‐carboxamides, namely N,N′‐(propane‐1,3‐diyl)bis(pyridine‐2‐carboxamide), C₁₅H₁₆N₄O₂, (I), and N,N′‐(butane‐1,4‐diyl)bis(pyridine‐2‐carboxamide), C₁₆H₁₈N₄O₂, (II), exhibit extended hydrogen‐bonded sequences involving their amide groups. In (I), conventional bifurcated amide–carbonyl (N—H)...O hydrogen bonding favours the formation of one‐dimensional chains, the axes of which run parallel to [001]. Unconventional bifurcated pyridine–carbonyl C—H...O hydrogen bonding links adjacent one‐dimensional chains to form a `porous' three‐dimensional lattice with interconnected, yet unfilled, voids of 60.6 (2) ų which combine into channels that run parallel to, and include, [001]. 4% of the unit‐cell volume of (I) is vacant. Compound (II) adopts a Z‐shaped conformation with inversion symmetry, and exhibits an extended structure comprising one‐dimensional hydrogen‐bonded chains along [100] in which individual molecules are linked by complementary pairs of amide N—H...O hydrogen bonds. These hydrogen‐bonded chains interlock viaπ–π interactions between pyridine rings of neighbouring molecules to form sheets parallel with (010); each sheet is one Z‐shaped molecule thick and separated from the next sheet by the b‐axis dimension [7.2734 (4) Å].     

Effect of the Hydration Shell on the Carbonyl Vibration in the Ala-Leu-Ala-Leu Peptide

The vibrational spectrum of the Ala-Leu-Ala-Leu peptide in solution, computed from first-principles simulations, shows a prominent band in the amide I region that is assigned to stretching of carbonyl groups. Close inspection reveals combined but slightly different contributions by the three carbonyl groups of the peptide. The shift in their exact vibrational signature is in agreement with the different probabilities of these groups to form hydrogen bonds with the solvent. The central carbonyl group has a hydrogen bond probability intermediate to the other two groups due to interchanges between different hydrogen-bonded states. Analysis of the interaction energies of individual water molecules with that group shows that shifts in its frequency are directly related to the interactions with the water molecules in the first hydration shell. The interaction strength is well correlated with the hydrogen bond distance and hydrogen bond angle, though there is no perfect match, allowing geometrical criteria for hydrogen bonds to be used as long as the sampling is sufficient to consider averages. The hydrogen bond state of a carbonyl group can therefore serve as an indicator of the solvent’s effect on the vibrational frequency.     

Crystal and molecular structure of 5,5-dimethyl-δ1-1,2,4-triazolin-3-one

The spectroscopic and X-ray data of the title compound are presented and discussed. Some anomalies are attributed to the lack of conjugation between the diazene and carbonyl group, and to the association of the molecules in the solid state through an unusual intermolecular hydrogen bond between the amide nitrogen atom and the diazene nitrogen atom N2.     

Novel ion-pair receptors based on hexahomotrioxacalix[3]arene derivatives

A series of novel heteroditopic hexahomotrioxacalix[3]arene triamide receptors capable of binding an anion and cation simultaneously in a cooperative fashion has been prepared. The lower rim functionalized cone-hexahomotrioxacalix[3]arene derivatives cone-5a-5d bearing three amide groups were synthesized from cone-3 by a stepwise reaction. The crystal structures of 5c and 5d and (1)H NMR studies in nonpolar solvents strongly indicate that a number of interesting intramolecular hydrogen bonding interactions exist in these receptors. The binding abilities of these compounds towards n-butylammonium chloride and bromide salts have been investigated using (1)H NMR titration experiments in CDCl(3) solvent. Owing to the 'flattened cone' conformations and intramolecular hydrogen bonding involving the amide NH and neighbouring O atoms in cone-5a-5d, the affinities toward n-Bu(4)NX (X = Cl(-) and Br(-)) were weakened. However, it should be noted that triamides cone-5a-5d show a single selectivity for halide anions in the presence of n-BuNH(3)(+) through intermolecular hydrogen bonding with the amide NH hydrogen atoms in the receptors in CDCl(3) solution. Association constants were calculated from the chemical shift changes of the amide protons.     

Stochastic model for the reorientation of molecules around their long axes in a smectic C phase

In smectic phases molecules can reorientate around their long and short axes. The motion of a molecule around its long axis is non-cooperative and influenced by both stochastic and deterministic forces exerted by neighbouring molecules. Solving the Smoluchovsky equation for such a reorientation process, two-time correlation functions are calculated which are related to frequency-dependent susceptibilities. The results are used for investigating how deterministic forces in higher ordered smectic phases have an effect on microwave spectra. It can be concluded that the quadrupolar ordering produces a splitting of the relaxation frequency. This splitting, which should occur at the transition from the smectic A to the smectic C phase, is only weakly influenced by an additional dipolar (ferroelectric) ordering.     

Rhodium(II)‐Catalyzed Enantioselective Synthesis of Troponoids

We report a rhodium(II)‐catalyzed highly enantioselective 1,3‐dipolar cycloaddition reaction between the carbonyl moiety of tropone and carbonyl ylides to afford troponoids in good to high yields with excellent enantioselectivity. We demonstrate that α‐diazoketone‐derived carbonyl ylides, in contrast to carbonyl ylides derived from diazodiketoesters, undergo [6+3] cycloaddition reactions with tropone to yield the corresponding bridged heterocycles with excellent stereoselectivity.     

Intramolecular hydrogen bonding in imidazole-4(5)-alkoxycarbonyl-5(4)-carboxamide derivatives

The ir spectrum of imidazole derivatives, which have an alkoxycarbonyl group and a carboxamide group at the 4- and 5-positions of the imidazole ring respectively, exhibits the shift of the ester carbonyl band to a lower wave number. This phenomenon was investigated by spectroscopic measurements of a group of relevant compounds. The results indicate that the shift is caused by the intramolecular hydrogen bonds between the hydrogen atom of the amide and the carbonyl oxygen of the ester which is enhanced by the resonance stabilization of the imidazole ring.     

Piv‐Proψ[CH2–NH–O]Gly–NHiPr

The pseudodipeptide, (S)‐N‐iso­propyl {[N‐(pivaloyl)­pyrrol­idin‐2‐yl]­methyl­amino­oxy}acet­amide, C₁₅H₂₉N₃O₃, adopts a global extended conformation with the hydroxy­l­amine group in the g⁺/g^? structure. The C‐terminal amide NH interacts intramolecularly with the hydroxy­lamine O atom. Both NH bonds of each mol­ecule are hydrogen bonded to the C‐­terminal amide carbonyl of a neighbouring mol­ecule.     

Molecular assembly of C2-symmetric Bis-(2S)-2-methyldodecanoylamides of alpha,omega-alkylidenediamines into coiled coil and twisted ribbon aggregates

A series of 10 didodecanoylamides of alpha,omega-alkylidenediamines bridged by a straight carbon chain varying in length from 0 to 9 carbons was examined as possible gelator molecules of organic liquids to gain information on the relationships between the spacial arrangement of two amide groups in a molecule and their effects on the microscopic structures of the gel. The structural characteristics of these amides are parallel and antiparallel arrangements of two amide carbonyl groups, which depend on the even and odd numbers of a bridging zigzag carbon chain. The linear alkyl chain moieties and a center carbon chain of diamides intermolecularly interact with each other within the van der Waals contact. Two amide moieties of an even number carbon chain diamide intermolecularly interact with each other by using two pairs of hydrogen bonds with two other molecules in a plane, which formed ribbonlike self-complementarily assembled aggregates. On the other hand, a diamide of an odd number carbon chain forms four independent hydrogen bonds with four other molecules not in a plane, which assembled into woven aggregates. Asymmetric introduction of a methyl group at the alpha-position of the amide groups successfully twists the two side chain van der Waals cores of the chiral diamides in the fixed direction, giving helically twisted ribbon and coiled coil aggregates. The helically twisted ribbon and coiled coil aggregates of these chiral diamides were directly observed by CD, SEM, and TEM, providing a basis for the design of a sophisticated small molecular gelator of a tailor-made shape.