Dilatometric Study of the Kinetics of the Polymerization of Pure meta-and Pure para-Divinylbenzenes

Abstract

A comparison of the dilatometrically determined rates of polymerization of pure meta-and pure para-divinylbenzenes confirms the previous observation that the meta isomer polymerizes more rapidly than the para isomer. This difference shows up also in the initiator square root rate dependencies, the gel times, and the conversions at gel point. The effect of added regulator (carbon tetrabromide) on the polymerization of the meta isomer is to decrease the gel time and conversion at gel time.     

The Thermal Dissociation of Phenol-Blocked Toluene Diisocyanate Crosslinkers

Abstract

The thermal dissociation reaction of different phenol-blocked toluene diisocyanate crosslinkers has been studied by the use of differential scanning calorimetry. It was found that dissociation occurs after melting of the adduct. The dissociation reaction rate constants, activation energies, and the heat of reaction values are reported. Adducts with orthosubstituted phenols dissociate at a faster rate than those with para isomers. The regeneration of isocyanate functionality was identified by an infrared spectrophotometer.     

Effect of aromatic substitution on the cure reaction and network properties of anhydride cured triphenyl ether tetraglycidyl epoxy resins

A systemic study of the impact of aromatic substitution on the reaction rate and network properties of the isomers of a tetraglycidylaniline triphenyl ether epoxy resin cured with anhydride hardeners is presented here. The epoxy resins synthesized in this work were based upon N,N,N,N‐tetraglycidyl bis(aminophenoxy)benzene (TGAPB), where the glycidyl aniline and ether groups change from being all meta (133 TGAPB), to meta and para (134 TGAPB), and finally to an all para substituted epoxy resin (144 TGAPB). Increasing para substitution increased reaction rate, promoted the onset of vitrification and increased epoxide conversion. Thermal properties such as glass transition temperatures (T_g) and coefficients of thermal expansion (CTE) both increased consistently with increasing para substitution, although thermal stability as measured via thermogravimetric analysis decreased. Mechanical properties also varied systematically with flexural strength and ductility increasing with increased para substitution, while the modulus decreased. Indeed, the ductility almost doubled, as measured by the work of fracture and displacement at failure highlighting the importance of substitution on properties.     

Chloromethylstyrene: Synthesis,Polymerization, Transformations,Applications

Abstract

Although scarcely used before 1972, chlororaethylstyrenes (ortho, meta, and para) have been the subject of an increasing number of publications and patents since then: 5 publications in 1972, 22 in 1973, 29 in 1976. The yearly average is now about 40 publications.     

Probing director fluctuations in nematic solutions by N.M.R. The breakdown of the simple RD + DF model for tolan in nematic Phase V

Abstract

Frequency dependent relaxation measurements have been carried out on the para deuterons of tolan-d ₁₀ (diphenylethyne), dissolved in Merck Phase V. The results are compared with those of three smaller probe molecules, studied previously. The simple RD + DF model which works well for the smaller probes, cannot give a satisfactory explanation for the relaxation behaviour, in particular the strong relaxation dispersion, of the para deuterons of tolan. The simple RD + DF model does not account properly for the effects of director fluctuations if the degree of orientation of the probe molecule studied is too high; this appears to be the case for tolan.     

N-BROMOSUCCINIMIDE-CATALYSED TRANSESTERIFICATION AND RACEMIZATION OF SULPHINATES

Abstract

Both aliphatic and aromatic sulphinates undergo transesterification reaction in the presence of N-bromosuccinimide. Isopropanolysis of optically active alkyl arenesulphinates was found to give racemic isopropyl arenesulphinates. The rate of racemization of optically active isopropyl p-toluenesulphinate was found to be first order with respect to both N-bromosuccinimide and isopropyl alcohol, suggesting that the reaction is a bimolecular nucleophilic substitution at the sulphur atom. The para electrodonating substituents in the aromatic ring accelerate slightly the rate of racemization. At the same time the rate of racemization was found to be retarded by the increase of steric requirements of the substituent at the sulphinyl sulphur atom suggesting that the initial formation of bromoxonium salt is the rate-determining step. Completely nonstereospecific isopropanolysis of optically active alkyl p-toluenesulphinates suggests that a sulphurane is formed as an intermediate in the exchange step of the reaction.     

The influence of perchloric acid on 2,3-dimethylpyrazine and 1,2-bis(4-pyridyl)ethane: crystal structure and Hirshfeld surfaces analysis

2,3-Dimethylpyrazine and 1,2-bis(4-pyridyl)ethane are both N-containing aromatic heterocyclics with two N atoms approximately in the para position. We here report two compounds derived from these heterocyclics (compounds 1 and 2). Compounds 1 and 2 both form a 1:1 2,3-dimethylpyrazine:perchloric acid (PA) and 1,2-bis(4-pyridyl)ethane:PA cocrystal, respectively. Their crystal structures were characterized by single-crystal X-ray diffraction, which revealed that the C–H?O and N–H?O hydrogen bonding interactions were found to stabilize the crystal structure in compounds 1 and 2. However, PA plays a necessary role for the one-dimensional structure in 1 and the three-dimensional structure in 2. Hirshfeld surfaces and fingerprint plots were applied to get the same conclusion.

     

THE SULFENAMIDE CHIRAL UNIT. TORSIONAL BARRIERS IN TRINITROBENZENESULFENAMIDES AND PERHALOBENZENSULFENAMIDES

Abstract

The free energies of activation for degenerate racemization of sulfenamides, measured by DNMR spectroscopy provide information about the N-S formal single bond since stereomutation is accomplished by torsion about this bond. The S-N torsional barrier in benzenesulfenamides (arSNR¹R²) is singnificantly increased by the presence of substituents which are electron withdrawin (by resonance). However, while the barrier is increased by para and^a/single ortho substituent, the introduction of a second ortho substituent lowers the barrier.     

Efficient Synthesis of Molecular Precursors for Para‐Hydrogen‐Induced Polarization of Ethyl Acetate‐1‐13C and Beyond

A scalable and versatile methodology for production of vinylated carboxylic compounds with ¹³C isotopic label in C1 position is described. It allowed synthesis of vinyl acetate‐1‐¹³C, which is a precursor for preparation of ¹³C hyperpolarized ethyl acetate‐1‐¹³C, which provides a convenient vehicle for potential in vivo delivery of hyperpolarized acetate to probe metabolism in living organisms. Kinetics of vinyl acetate molecular hydrogenation and polarization transfer from para‐hydrogen to ¹³C via magnetic field cycling were investigated. Nascent proton nuclear spin polarization (%P_H) of ca. 3.3 % and carbon‐13 polarization (%P_13C) of ca. 1.8 % were achieved in ethyl acetate utilizing 50 % para‐hydrogen corresponding to ca. 50 % polarization transfer efficiency. The use of nearly 100% para‐hydrogen and the improvements of %P_H of para‐hydrogen‐nascent protons may enable production of ¹³C hyperpolarized contrast agents with %P_13C of 20–50 % in seconds using this chemistry.     

The Oxidation of Guaiacol,Serotonin, o-Cresol,p-Cresol,m-Cresol,Homovanillic Acid,and m-Tyrosine by Horseradish Peroxidase and Hydrogen Peroxide

Abstract

A survey of 14 substrates for the fluorometric determination of the oxidative enzyme-horseradish peroxidase was carried out. The compounds which seemed to act well as substrates are serotonin, guaiacol, o-cresol, p-cresol, m-cresol, homovanillic acid and m-tyrosine. L-Epinephrine, equilenin, equilin, β-estradiol, estriol, and estrone were studied and found not to be substrates of the system.

The kinetics of the oxidation reactions were studied. They followed the Michaelis constant rate equation. The Michaelis constant, Km, was determined by a Lineweaver-Burk plot for each substrate.

It would appear that the presence of a group in the ortho, para, or meta position of the phenolic ring decreases the binding of the subtrate to the enzyme's active site, as shown by the km values obtained. It may be concluded that m-tyrosine is the best substrate (lowest km value) when compared to all the substrates which have been studied to date by the authors.     

Preparation,crystal structures and properties of half-sandwich ruthenium complexes containing salicylbenzoxazole ligands

Three half-sandwich ruthenium complexes [Ru(p-cymene)LCl] containing salicylbenzoxazole ligands [LH = 2-(5-methyl-benzoxazol-2-yl)-4-methyl-phenol (2a), LH = 2-(5-methyl-benzoxazol-2-yl)-4-chloro-phenol (2b), and LH = 2-(5-methyl-benzoxazol-2-yl)-4-bromo-phenol (2c)] were synthesized and characterized. All half-sandwich ruthenium complexes were fully characterized by ¹H and ¹³C NMR spectra, MS, elemental analyses, and UV–vis as well as cyclic voltammetry (CV). The molecular structures of 2a, 2b, and 2c were confirmed by single-crystal X-ray diffraction. Single-crystal X-ray structures show that the synthesized ruthenium complexes are three-legged piano-stools with a six-membered metallocycle formed by coordination of the bidentate salicylbenzoxazole ligands to the metal centers. Data from CV and UV–vis absorption of the ruthenium complexes indicated that by changing the substituent on the para position of (donating or withdraw group) the salicylbenzoxazole ligands, minor changes in redox and electronic properties of the ruthenium complexes were observed.     

Transition metal-catalyzed olefin arylation via C–H bond activation of arenes

In this article, two kinds of our transition metal-catalyzed olefin arylations are summarized and discussed. The first one is Ir-catalyzed novel anti-Markovnikov hydroarylation of olefins with benzene. Using this reaction catalyzed by [Ir(μ-acac-O,O′,C₃)(acac-O,O′)(acac-C₃)]₂ (acac = acetylacetonato), 1, straight-chain alkylarenes, which were not obtainable by the conventional Friedel-Crafts aromatic alkylation with olefins, were able to be successfully synthesized directly from arenes and olefins with the higher selectivity than that of branched alkylarenes. This is the first efficient catalyst which shows the desirable high regioselectivity. The reaction of benzene with propylene gave n-propylbenzene and cumene in 61% and 39% selectivities, respectively, and the reaction of benzene and styrene afforded 1,2-diphenylethane in 98% selectivity. The reaction of alkylarene and olefin showed meta and para orientations. A wide range of olefins and arenes can be employed for the synthesis of alkylarenes. The mechanism of the reaction involves C–H bond activation of benzene by Ir center to form Ir–phenyl species. The second reaction is Rh-catalyzed oxidative arylation of ethylene with benzene to directly produce styrene, namely one-step synthesis of styrene. The reaction of benzene with ethylene catalyzed by Rh(ppy)₂(OAc) (ppyH = 2-phenylpyridine, OAc = acetate), 3 with Cu oxidizing agent gave styrene and vinyl acetate in 77% and 23% selectivities, respectively, in contrast to those by Pd(OAc)₂, 47% of styrene and 53% of vinyl acetate. The mechanism of the reaction involves Rh-mediated C–H bond activation of benzene, which appears to be a rate-determining step. Furthermore, Rh complexes in a Rh(I) oxidation state at the beginning of the reaction work as catalysts for the reaction by addition of acacH and O₂ without any oxidizing agent, like Cu salt.     

Inductive effect for the phase stability in hydrogen bonded liquid crystals,x-(p/m)BA:9OBAs

A new series of hydrogen bonded liquid crystal (HBLC) complexes, made up with substituted benzoic acids (BAs) and nonyloxy benzoic acid, viz., x-(p/m)BA:9OBAs are reported for x = F, Cl, Br and –CH₃ substituted at para (p) or meta (m) positions of BA moiety. Proton nuclear magnetic resonance (¹H-NMR) spectrum confirms the HBLC complex. Infra red (IR) spectrum confirms linear, double and complementary type of hydrogen bonding (HB) between x-(p/m)BAs and 9OBA. The liquid crystal (LC) phases are characterised by polarisation optical microscopy (POM) and differential scanning calorimetry (DSC) techniques. x-(p/m)BA:9OBA exhibit N, C and G LC phase variance. HB induces tilted phases and enhances LC phase stability. The influence of configuration, size, electronegativity, electron directing capacity and inductive nature of substituent (x) is investigated for the stability of LC phases. An overview of the LC phase data indicates predominant ‘negative inductive effect’ in HBLCs with electron withdrawing substituents. Inductive effect operates effectively for para substitutions. Results are discussed in the wake of reports in other HBLCs.     

Butyrolactones derivatives from the fermentation products of a plant entophytic fungus Penicillium oxalicum

Two new butyrolactone derivatives, terrelactones A and B (1 and 2), together with four known butyrolactone derivatives (3–6), were isolated from the fermentation products of the fungus Penicillium oxalicum 0403. Their structures were elucidated by spectroscopic methods, including extensive 1D and 2D NMR techniques. The anti-tobacco mosaic virus (anti-TMV) activities of 1 and 2 were evaluated. The results showed that compounds 1 and 2 exhibited high anti-TMV activity with inhibition rates of 25.5% and 27.4%, respectively. The inhibition rate is close to that of positive control (28.9%).     

NMR and FTIR investigation of the solution imidization kinetics of model compounds of PMDA/ODA polyamic ethyl ester

Meta- and para-diethyl-p,p-oxydiphenylene pyromellitamide (DOP), the model compounds of the meta and para PMDA/ODA polyamic ethyl ester, were synthesized and characterized by NMR and FTIR spectroscopy. Investigation of the imidization in d₆-DMSO solution using NMR and FTIR techniques has shown that both the half imide and imide were formed. Quantitative analysis of the curing rates and degrees of conversion of the isomers in dilute d₆-DMSO solution as a function of time under isothermal conditions or as function of temperature at fixed time (1 h) indicated that the kinetics of the ring closure reaction of the meta and para isomers were the same within 10%. This suggests that intrinsic reactivity differences between the isomers do not have much effect on the imidization process and do not account for the differences in rate that have been observed for the meta and para polymers in the solid state. No interconversion between the two isomeric forms occurred below 180°C, as has been observed for polyamic acids and their model compounds. The degree of conversion strongly depended on the reaction temperature and increased quickly after 170°C. The rate constant of the second ring closure reaction was found to be approximately three to four times the rate constant of the first ring closure reaction. © 1996 John Wiley & Sons, Inc.     

Photochemical Transformation of Colchicine: A Kinetic Study

Spectroscopic methods and theoretical calculations were used to study the photophysical properties of colchicine (1). The characteristic bands of colchicine (1) transitions occurring at ∼245 nm and 350 nm arise from n–π ^* and π–π ^* transitions, and were found to be blue shifted with increasing polarity index of the solvent and red shifted (bathocrhomic) with increasing acidity of the media. Solvent type and polarity were found to affect both the rate constant and photo conversion yield. Excitation of colchicine (1) at 366 nm populates the S1 orbital, from which the photoreaction of colchicine (1) initially produces lumicolchicine directly in its ground state by a concerted disrotatory electrocyclization (i.e., 4π electrocyclization involving the tropolone ring). The acidity of the media affects both rate constants and conversion yield; both of these were inversely proportional to the acid concentration. The presence of acid decreases the photo conversion yield of colchicine (1) from 90% to 40%. The ionic strength affects both the rate constants and the photo conversion yield; rate constants are inversely related to the ionic strength. The photochemistry of colchicine (1) is explained on the basis of the initial formation of a solvation complex in the ground state.     

Substituent Effects in High-Performance Liquid Chromatography of Diarylacrylonitriles

Abstract

Thirty diarylacrylonitriles, carrying various para substituents in the phenyl ring attached to the position l of the ethylenic bridge and various heterorings (thienyl, furyl, pyrryl, N-methylpyrryl) attached to the position 2, have been investigated on silica gel. An additional substituent is present in the thienyl derivatives. The capacity factors of all the compounds can be grouped in only five or six families, according to the variation in the para-phenyl substitution or in the heteroring moiety, respectively. The strongest effect in the enhancement of the capacity factors is given by a methoxy or nitro group in the para-phenyl position.

Other minor effects as well as the relationship between capacity factors and solvent mixtures polarity are discussed.     

Study of the Fischer cyclization of diarylhydrazones and related secondary hydrazones I. Relative orienting capacity of the p-methyl and p-methoxy groups of diarylhydrazines

A mixture of isomeric N-arylindoles is formed in the Fischer cyclization of N,N-diphenyllydrazones variously substituted in the para position by CH₃ or CH₃O groups. The intramolecular competition method makes it possible to form a judgment regarding the relative orienting capacity of the substituents in the aromatic ring in the step involving rearrangement of the enamine form of the hydrazone; in this case the effect of the rate of protonation and tautomerization of the hydrazone is excluded. It was established that the rate of rearrangement increases for the para substituents in the order H< CH₃< CH₃O.     

Substituent Effects on 31P and 13C Chemical Shifts of Substituted Diphenyl 1-anilino-1-arylmethanephosphonates and Their Anions

Abstract

For a series of 31 novel diphenyl 1-anilino-1-arylmethanephosphonates, substituted in the meta and para position of the anilino and/or the aryl ring, ³¹P chemical shifts show good linear correlation with Taft's [sgrave]° parameters, the ³¹P nucleus appearing better shielded in the case of electron-withdrawing substituents. This inverse relationship is due to a field effect of the substituent dipole which polarizes π-electron clouds in the molecule, resulting in a higher P=O double bond order, and thence better ³¹P shielding. A corresponding shift of π-electron density is likewise observed for the ¹³C resonances of the two diastereotopic phenoxy and the anilino or aryl rings, respectively, where-M ands-I substituents cause a downfield shift of para and meta, and an upfield shift of ortho and ipso carbon resonances.