Mechanism of reaction of phenyl glycidyl ether with phenyl benzoate in the presence of water

The reaction of phenyl glycidyl ether with phenyl benzoate in the presence of water was investigated by adsorption liquid chromatography.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 131–133, January, 1990.     

Spectroscopic and conformational study of phenyl benzoate

IR spectra of phenyl benzoate (PB) have been studied at various temperatures. On the basis of the calculation of the frequencies and forms of the normal phenyl benzoate molecule, the complete assignment of vibrational spectra was achieved. A conformational analysis of PB was carried out using molecular mechanics calculations. It was shown that the relative orientation of the benzene rings varies with temperature and phase state.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 459–463, March, 1995.     

Melting and spherulitic crystallization of a phenyl benzoate

Melting and solidification of BPC (butyl p-(p-ethoxyphenoxy-carbonyl)phenylcarbonate) have been studied by polarization microscopy and differential scanning calorimetry. BPC can exist at room temperature in two different crystallographic modifications which melt directly into the nematic state at different temperatures (c. 330·5 K and 338·5 K). The nematic fluid crystallizes below c. 313 K to form simultaneously two types of spherulitic aggregates corresponding to the two crystal types. Both the spherulites possess a positive birefringence; but they vary significantly in their morphological and kinetic aspects. Further, in one of them the molecular long axes are radial, while in the other they are tangential. This fact emerges from optical and electrooptical observations on the pseudomorphic nematic domains obtained by melting the spherulites. Above 313 K, the crystals that grow are nonspherulitic, lamellar, biaxial and optically positive; they melt at c. 338·5 K. The glassy nematic state is realised by rapidly quenching the melt to a low temperature (100 K). On heating, the glassy state transforms into the supercooled nematic state near 234·5 K.     

Gradient flexoelectric switching response in a nematic phenyl benzoate

We report on the inverse flexoelectric effects observed in a nematic liquid crystal with a small positive dielectric anisotropy subject to static and very low frequency (<1 Hz) a.c. fields. The Bobylev–Pikin flexobands appear at a temperature‐dependent d.c. threshold. Under square wave excitation, a new type of transient optical response occurs soon after each polarity reversal, and we ascribe it to the gradient flexoelectric distortion explicable on the basis of the presence of intrinsic double layers. This instability is characterized by a threshold voltage that decreases with temperature. Its maximum amplitude increases linearly with voltage close to threshold, and occurs after polarity reversal at a time τ_m that scales inversely as the voltage; τ_m decreases exponentially with frequency and temperature. After each polarity change, the ionic current following the charging current decreases almost exponentially to a non‐zero value; the residual current increases monotonically with the applied bias.     

Photochemical rearrangement of phenyl benzoate in the presence of cyclodextrins and amylose

The photorearrangement of phenyl benzoate in aqueous medium is changed in the presence of cyclodextrins or amylose; the ortho/para migration ratio is altered in favor of the para position.     

Monolayer behaviour of a nematogenic phenyl benzoate at the air-water interface

The pressure-area characteristics of the monolayers of butyl p-(p--ethoxy-phenoxycarbonyl) phenyl carbonate (BPC) have been studied at various temperatures in the range 10°-31°C. With compression, the film passes from the gaseous (G) to the multilayer (M) state, via the liquid condensed (L) state. The transitions from G to L and L to M states occur over wide plateau regions at lower temperatures. The widths of these regions and also the molecular areas at which they begin decrease linearly with elevation in temperature. A remarkable feature of the isotherms is that, in the G and L regions, as the temperature is lowered, they shift in the direction of higher pressure. This is explained by taking into account the possible molecular orientations with respect to the substrate. The overall surface behaviour of BPC differs from that of some other phenyl benzoates studied earlier. In particular, BPC does not form liquid-crystal-like multilayers. The paper also includes certain results on the surface behaviour of mixtures of BPC and cholesterol; the condensing effect of cholesterol is briefly discussed.     

Chiral liquid-crystalline copolyacrylates with biphenyl and phenyl benzoate side groups

The phase behavior and structure of liquid-crystalline phases of three series of copolymers with mesogenic units belonging to the families of biphenyls and phenyl benzoates have been studied, with the former mesogenic units containing a chiral center in a flexible spacer. A variation in the isotropization temperature as a function of composition is well described by the additivity rule, whereas the tilt angle of mesogenic groups in smectic layers changes nonlinearly. This angle decreases beginning from homopolymers and attains the minimum value for the copolymers of the equimolar composition, which show the highest ferroelectric activity among the polymer systems under study.     

Instabilities across the isotropic conductivity point in a nematic phenyl benzoate under AC driving

We characterize the sequence of bifurcations generated by ac fields in a nematic layer held between unidirectionally rubbed ITO electrodes. The material, which possesses a negative dielectric anisotropy epsilona and an inversion temperature for electrical conductivity anisotropy sigmaa, exhibits a monostable tilted alignment near TIN, the isotropic-nematic point. On cooling, an anchoring transition to the homeotropic configuration occurs close to the underlying smectic phase. The field experiments are performed for (i) negative sigmaa and homeotropic alignment, and (ii) weakly positive sigmaa and nearly homeotropic alignment. Under ac driving, the Freedericksz transition is followed by bifurcation into various patterned states. Among them are the striped states that seem to belong to the dielectric regime and localized hybrid instabilities. Very significantly, the patterned instabilities are not excited by dc fields, indicating their possible gradient flexoelectric origin. The Carr-Helfrich mechanism-based theories that take account of flexoelectric terms can explain the observed electroconvective effects only in part.     

Photophysical process of hexadecyl 4-biphenylamino benzoate

The photophysical properties of hexadecyl 4-biphenylamino benzoate (HBAB), the molecule of which possesses a polar end composed of donor (triphenylamino group) and acceptor (ester group) and a long non-polar alkyl tail, have been carefully studied in different conditions. The results show that the twisted intramolecular charge transfer (TICT) emission is given in polar solvents at room temperature and intramolecular charge transfer (ICT) emission is given at 77 K. These can be supported by the solvent effect, temperature effect and the quenching process.     

Influence of chirality on the mesophase of side chain polymers with phenyl benzoate pendant groups

To reveal the structure of an amorphous mesophase with a hidden liquid crystalline structure (ISm*) in a chiral side chain polymer, P8*M, its racemic isomer has been synthesized along with two more RS‐copolymers with controlled enantiomer excess. The phase behaviour of the copolymers was studied comparatively by DSC and X‐ray scattering. Optical rotatory dichroism was measured for thin films of P8*M and two homologue polymers, differing in the polymeric main chain, by the size of the chiral terminal group and by its absolute configuration. A helical superstructure with pitch of about 250?nm is indicated within the ISm* mesophase. Its structure as a short pitch TGB phase hase been proven conclusively.     

Influence of chirality on the mesophase of side chain polymers with phenyl benzoate pendant groups

To reveal the structure of an amorphous mesophase with a hidden liquid crystalline structure (ISm*) in a chiral side chain polymer, P8*M, its racemic isomer has been synthesized along with two more RS-copolymers with controlled enantiomer excess. The phase behaviour of the copolymers was studied comparatively by DSC and X-ray scattering. Optical rotatory dichroism was measured for thin films of P8*M and two homologue polymers, differing in the polymeric main chain, by the size of the chiral terminal group and by its absolute configuration. A helical superstructure with pitch of about 250 nm is indicated within the ISm* mesophase. Its structure as a short pitch TGB phase hase been proven conclusively.     

Mechanisms of the hydrogen atom and the phenyl group migration in the molecule of heptaphenylcycloheptatriene

In terms of the density functional theory using the B3LYP functional, 1,2,3,4,5,6,7-heptaphenylcycloheptatriene was shown to be the most stable in the boat conformation of the cycloheptatriene ring with the H atom in the equatorial position. 1,5-Sigmatropic shifts of the H atom along the seven-membered ring perimeter take place when it is in the axial position through the asymmetric transition state with the barrier ΔE ^≠ _ZPE = 28.7 kcal mol^?1. The H atom can attain the axial position upon inversion of the seven-membered ring, which is accompanied by the orthogonal turn of the phenyl group at the sp³-hybridized C atom (ΔE ^≠ _ZPE = 22.6 kcal mol^?1). The energy barrier to the circular rearrangement of the H atom (ΔE ^≠ _ZPE = 32.2 kcal mol^?1) explains formation of isomers during the high-temperature synthesis of di(p-tolyl)pentaphenylcycloheptatriene. The barrier to the 1,5-sigmatropic shifts of the phenyl group is 19.7 kcal mol^?1 higher than that for the competing shifts of the H atom.     

Synthesis of graphislactones A-D through a palladium-mediated biaryl coupling reaction of phenyl benzoate derivatives

The chemical synthesis of graphislactones A-D was achieved through the Pd-mediated intramolecular biaryl coupling reaction of phenyl benzoate derivatives.     

Formation of the diphenyl molecule in the crossed beam reaction of phenyl radicals with benzene

The chemical dynamics to form the D5-diphenyl molecule, C6H5C6D5, via the neutral-neutral reaction of phenyl radicals (C6H5) with D6-benzene (C6D6), was investigated in a crossed molecular beams experiment at a collision energy of 185 kJ mol(-1). The laboratory angular distribution and time-of-flight spectra of the C6H5C6D5 product were recorded at mass to charge mz of 159. Forward-convolution fitting of our data reveals that the reaction dynamics are governed by an initial addition of the phenyl radical to the pi electron density of the D6-benzene molecule yielding a short-lived C6H5C6D6 collision complex. The latter undergoes atomic deuterium elimination via a tight exit transition state located about 30 kJ mol(-1) above the separated reactants; the overall reaction to form D5-diphenyl from phenyl and D6-benzene was found to be weakly exoergic. The explicit identification of the D5-biphenyl molecules suggests that in high temperature combustion flames, a diphenyl molecule can be formed via a single collision event between a phenyl radical and a benzene molecule.     

The reversal of the diamagnetic anisotropy in amphiphilic nematic liquid crystals using the aromatic counterions phenyl sulphonate and benzoate

Proton N.M.R. is used to investigate the inclusion of the phenylsulphonate and the benzoate ion as counterions in samples of amphiphilic nematic liquid crystals. When these aromatic counterions are substituted in sufficient amounts the sign of the diamagnetic anisotropy is reversed. The orientation parameters are also shown to be dependent upon the micelle shape, as well as the sign of the diamagnetic anisotropy.     

Intramolecular biaryl coupling reaction of benzyl benzoate and phenyl benzoate derivatives, and its application to the formal synthesis of (−)-steganone

Construction of the biaryl moiety of stegane and related compounds through an intramolecular biaryl coupling reaction is described. Undesired products were obtained by the intramolecular coupling reaction of benzyl benzoates (8, 13, and 14) because of their steric and electrostatic properties, and only that of phenyl benzoates (26b and 26c) afforded the desired biaryl lactones in good yields. An asymmetric formal synthesis of the title compound has been achieved using an enantioselective lactone-opening reaction followed by a four-step conversion to the known compound.