Reaction of α-cellulose with SbCl3–KOH–AsCl3

α-Cellulose dissolves in a mixture of SbCl₃, KOH, and AsCl₃. The resulting product as identified by PMR and infrared spectroscopy is α-D -glucose. This product is unexpected, and an explanation for its formation is suggested.     

The structural (FTIR,XRD, and XPS) and biological studies of thermosensitive chitosan chloride gels with β‐glycerophosphate disodium

In this article, the properties of thermosensitive chitosan hydrogels (structural and biological) prepared using chitosan chloride and β‐glycerophosphate are presented. The porous structure of the gels was observed with a scanning electron microscopy (SEM). Rheological and other structural and morphological investigations were carried out by infrared spectroscopy and X‐ray photoelectron spectroscopy. Crystallinity of the gel was determined by X‐ray diffraction analysis. Biocompatibility of the chitosan gels was investigated by contact with bone cells (line Saos‐2) for 7 and 21 days. The cells were encapsulated and seeded onto the gel. A live/dead test showed no cytotoxic reaction. The structure of the gels, before and after the cell culture, was tested using SEM (including ESEM), to select the most suitable method of preparation and reliable visualization of the gel with cells. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46459.     

Pyrolysis products of untreated and flame retardant-treated α-cellulose and levoglucosan

A typical gas chromatogram of the volatile pyrolysis products of untreated α-cellulose contains 39 peaks; however, mass spectral data indicate that at least 59 compounds, with molecular weights less than about 150, are present. A total of 37 compounds have been identified, 13 of which have not been previously reported. Most of the newly identified compounds contain a benzene ring, indicating that these compounds may be products of reactions between initial volatiles. A comparison of the products generated in the temperature range of 330°–440°C indicates that the formation of pyrolysis products is essential independent of temperature. Comparisons of the chromatograms obtained for untreated levoglucosan and cellulose indicate that most of the decomposition of cellulose probably forms levoglucosan which then decomposes to yield the observed pyrolysis products. In addition, the products of flame retardant-treated levoglucosan are essentially the same as those of cellulose with the same retardant treatment. This suggests that the retardants act on the levoglucosan formed in the decomposition of the cellulose rather than on the cellulose directly.     

Poly(α,α,α′,α′-tetrafluoro-p-xylylene)

Poly(α,α,α′,α′-tetrafluoro-p-xylylene) was prepared by the pyrolysis of cyclo-di-(α,α,α′,α′-tetrafluoro-p-xylylene) and by the pyrolysis of α,α′-bis(alkylsulfonyl)-α,α,α′,α′-tetrafluoro-p-xylene. The pyrolysis of α,α′-dibromo-α,α,α′,α′-tetrafluoro-p-xylylene also gave the polymer, but the method is less satisfactory. Poly(α,α,α′,α′-tetrafluoro-p-xylylene) shows remarkable thermal and oxidative stability at elevated temperatures. Useful mechanical and electrical properties are retained after aging for 3000 hr at 250° in air. After initial change due to crystallization, tensile strength remains near 10,000 psi, elongation above 5%, and dielectric constants and dissipation factors at approximately 2.4 and .001, respectively.     

TPR and XRD studies of yttria-doped ceria/γ-alumina-supported copper oxide catalyst

Yttria-doped ceria (YDC) and pure ceria (CeO₂), respectively, were deposited on γ-alumina (γ-Al₂O₃) using the impregnation method; then, copper oxide was also supported on them by employing the impregnation method. For comparison, CuO/γ-Al₂O₃ catalysts were prepared in this work. The catalysts were characterized by temperature-programmed reduction (TPR) and X-ray diffraction (XRD). For CuO/γ-Al₂O₃ catalysts, two TPR peaks, namely β and γ, were observed. These have been attributed to the reduction of highly dispersed copper oxide species and bulk-like copper oxide, respectively. For CuO/CeO₂/γ-Al₂O₃ and CuO/YDC/γ-Al₂O₃ catalysts, four TPR peaks, namely ₁, ₂, β′ and γ′, could be observed. The peaks with lower peak temperatures as compared to those of β′ and γ′ peaks have been attributed to the reduction of interface-boundary copper oxide species that contact closely and interact strongly with the supported ceria or YDC. Crystal sizes calculated from XRD measurements confirmed that yttria (Y₂O₃) addition could lead to crystal growth of ceria and correspondingly enhance the dispersion of the supported copper oxide due to the partition of YDC crystallite. Hence, this work shows that supported YDC and ceria can act bi-functionally as a textural promoter as well as a structural promoter.     

Highly Stereoselective Halocyclopropanation of α,β‐Unsaturated Amides

A convenient highly stereoselective synthesis of chloro‐ and bromocyclopropanamides from di‐ tri‐ or tetrasubstituted (E)‐ or (Z)‐α,β‐unsaturated amides with total or high stereoselectivity promoted by chromium dichloride or dibromide is described. The transformation of chlorocyclopropanamides into the corresponding ketones or amines is also reported. A mechanism to explain these transformations is proposed.     

Grafting of poly(α-chloroacrylonitrile) (α-PCIAN) on carbon black and electrical properties of α-PCIAN-grafted carbon black compositions

The electrical properties of poly(α-chloroacrylonitrile) (PCIAN) carbon black compositions were determined. These materials were prepared by polymerizing α-chloroacrylonitrile in the presence of carbon black (GC resistors). Resistivities measurement of GC resistors shows a semiconductor-like behavior. Moreover, the resistance change of GC resistors with electrical field strength is very large. It is concluded that the conduction of GC resistors is controlled by the thin polymer layer present at the surface of the carbon black particles. Heat degradation of such compositions was also investigated: A significant weight loss above 150°C is observed in all cases which can be attributed to thermal dehydrochlorination of PCIAN. After heat treatment at 300°C, during 1 h, the resistivities decrease of about 1 order of magnitude because of the formation of a semiconducting polyconjugated polymer by dehydrochlorination of PCIAN.     

Interface formation of Ca with poly(p-phenylene α,α′-diphenyl vinylene) and poly(p-phenylene α-phenyl vinylene)

We have investigated the interface formation of Ca with poly(p-phenylene α,α′-diphenyl vinylene) (PPV-DP) and poly(p-phenylene α-phenyl vinylene) (PPV-P) using X-ray photoemission spectroscopy (XPS). Similarly to our earlier findings in metal/PPV interface formation, the O 1s peak shifted toward a lower binding energy as soon as Ca was deposited on to the polymers. This was accompanied by the formation of Ca? O, suggesting a chemical origin for the O 1s shift. By contrast, the C 1s peak shift toward a lower binding energy was observed relatively later, after about 4 Å of Ca deposition. At the same time, a new C 1s component became noticable at about ?1.5 eV relative to the initial C 1s peak. This component signifies the possibility of polymer disruption by the Ca atoms to form Ca? C species. The C 1s peak shift is attributed to Ca induced surface band bending and barrier formation as in the case of metal/PPV interface formation. The disruption of the polymer may also induce changes in the interface electronic states and contribute to the C 1s peak shift. From the intensity attenuation analysis, we conclude that the initial 15 Å of Ca overlayer is contaminated by the Ca? O and Ca? C species and the overlayer is pure beyond 15 Å of Ca coverage.     

Ein effektives Verfahren zur Herstellung von 1α,25-Dihydroxy-cholecalciferol (Calcitriol) aus 1α3β,25-Trihydroxy-cholesta-5,7-dien (Procalcitriol)

An Effective Procedure for the Synthesis of 1α,25-Dihydroxy-cholecalciferol (Calcitriol) Starting with 1α,3β, 25-Trihydroxy-cholesta-5,7-diene (Pro-Calcitriol) In order to develop an effective synthesis of the important vitamin D metabolite 1α,25-(OH)₂-cholecalciferol (calcitriol) 5a starting with pro-calcitriol 1a the influence of reaction temperature and degree of turnover of 1a to the compositions of the photoproducts at irradiation in a 500 ml photoreactor were investigated. The combination of the highly photostable filter solution consisting of 2,7-dimethyl-3,6-diaza-cyclohepta-1,6-diene-tetrafluoroborate and biphenyl in ethanol realizes the double wavelength irradiation in the range of 290 to 300 nm and > 330 nm resulting in a highly amount of the desired pre-calcitriol 2a . The reversible photoisomers of pre-calcitriol 2a 1α,25-(OH)₂-lumisterol₃ 4a and 1α,25-(OH)₂-tachysterol₃ 3a were isolated from an irradiation mixture in pure form by means of an appropriate combination of flash-chromatography, MPLC and preparative HPLC, respectively. The isomers 2a, 3a and 4a were characterized chromatographically and spectroscopically. Photoisomerization of 1a at −45 °C using the filter solution mentioned above and recycling all reversible photoisomers resulted in highly pure 5a after thermally induced isomerization of 2a isolated from the irradiation mixture by means of flash-chromatography on Ag⁺- impregnated silica with a yield of 68%.     

An efficient Synthesis of Acetylenic γ- and δ-Hydroxy Ketones, γ- and δ-keto acids,and γ- diketones via addition of 1-alkinyllithium compounds to γ- and δ-lactones

2-Hydroxy-6-alkyn-5-ones 3 , 1-hydroxy-5-alkyn-4-ones 4 , and 1-hydroxy-6-alkyn-5-ones 5 are conveniently obtained in excellent yields through a highly selective monoaddition of an 1-alkynyllithium compound 2 to γ-valerolactone (1a) , γ-butyrolactone (1b) or δ-valerolactone (1c) . They are oxidized by pyridinium dichromate or Jones reagent to the corresponding acetylenic 1,4-diketones 6 , 4-oxo carboxylic acids 7 , and 5-oxo carboxylic acids 8 , respectively.     

Organocatalytic Highly Enantioselective Synthesis of β‐Formyl‐α‐hydroxyphosphonates

The cross‐aldol reaction between enolizable aldehydes and α‐ketophosphonates was achieved for the first time by using 9‐amino‐9‐deoxy‐epi‐quinine as the catalyst. β‐Formyl‐α‐hydroxyphosphonates were obtained in high to excellent enantioselectivities. The reaction works especially well with acetaldehyde, which is a tough substrate for organocatalyzed cross‐aldol reactions. The products were demonstrated to have anticancer activities.     

One‐Step Catalytic Enantioselective α‐Quaternary 5‐Hydroxyproline Synthesis: An Asymmetric Entry to Highly Functionalized α‐Quaternary Proline Derivatives

The highly enantioselective cascade reaction between N‐protected α‐cyanoglycine esters and α,β‐unsaturated aldehydes is disclosed. The reaction represents a one‐step entry to polysubstituted 5‐hydroxyproline derivatives having a quaternary α‐stereocenter generally in high yields with up to >95:5 dr and 99:1 er. It is also a direct catalytic two‐step entry to functionalized α‐quaternary proline derivatives.     

Highly Enantioselective Michael Addition of α‐Substituted Cyano Ketones to β,γ‐Unsaturated α‐Keto Esters using Bifunctional Thiourea‐Tertiary Amine Catalysts: An Easy Access to Chiral Dihydropyrans

An asymmetric Michael addition of α‐substituted cyano ketones to β,γ‐unsaturated α‐keto esters to form chiral dihydropyrans catalyzed by a series of α‐amino acid‐derived thiourea‐tertiary amines is presented. A novel tyrosine‐derived thiourea catalyst was identified as the optimal catalyst providing the desired product in 91–95% yields and with 90–96% ee at a low catalyst loading of 2.0 mol%. The utility of the reaction was exemplified by facile conversion of the dihydropyran product into pharmaceutically useful dihydropyridine.     

Cationic copolymers of α,β‐poly‐(N‐2‐hydroxyethyl)‐DL‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy): synthesis and characterization

In the present study the derivatization of two water‐soluble synthetic polymers, α,β‐poly(N‐2‐hydroxyethyl)‐DL ‐aspartamide (PHEA) and α,β‐polyasparthylhydrazide (PAHy), with glycidyltrimethylammonium chloride (GTA) is described. This reaction permits the introduction of positive charges in the macromolecular chains of PHEA and PAHy in order to make easier the electrostatic interaction with DNA. Different parameters affect the reaction of derivatization, such as GTA concentration and reaction time. PHEA reacts partially and slowly with GTA; on the contrary the reaction of PAHy with GTA is more rapid and extensive. The derivatization of PHEA and PAHy with GTA is a convenient method to introduce positive groups in their chains and it permits the preparation of interpolyelectrolyte complexes with DNA. © 2000 Society of Chemical Industry     

Ethylene/α‐olefin copolymerization by nonbridged (cyclopentadienyl)(aryloxy)titanium(IV) dichloride/AliBu3/Ph3CB(C6F5)4 catalyst systems

A series of nonbridged (cyclopentadienyl) (aryloxy)titanium(IV) complexes of the type, (η⁵‐Cp′)(OAr)TiCl₂ [OAr = O‐2,4,6‐^tBu₃C₆H₂ and Cp′ = Me₅C₅ ( 1 ), Me₄PhC₅ ( 2 ), and 1,2‐Ph₂‐4‐MeC₅H₂ ( 3 )], were prepared and used for the copolymerization of ethylene with α‐olefins (e.g., 1‐hexene, 1‐octene, and 1‐octadecene) in presence of AlⁱBu₃ and Ph₃CB(C₆F₅)₄ (TIBA/B). The effect of the catalyst structure, comonomer, and reaction conditions on the catalytic activity, comonomer incorporation, and molecular weight of the produced copolymers was examined. The substituents on the cyclopentadienyl group of the ligand in 1 – 3 play an important role in the catalytic activity and comonomer incorporation. The 1 /TIBA/B catalyst system exhibits the highest catalytic activity, while the 3 /TIBA/B catalyst system yields copolymers with the highest comonomer incorporation under the same conditions. The reactivity ratio product values are smaller than those by ordinary metallocene type, which indicates that the copolymerization of ethylene with 1‐hexene, 1‐octene, and 1‐octadecene by the 1–3/ TIBA/B catalyst systems does not proceed in a random manner. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of polypseudorotaxanes and polyrotaxanes with multiple α- and γ-cyclodextrins co-threaded over poly[(ethylene oxide)-ran-(propylene oxide)]

A series of novel polypseudorotaxanes, in which multiple α-cyclodextrin (α-CD) and γ-cyclodextrin (γ-CD) rings were randomly co-threaded over a poly[(ethylene oxide)-ran-(propylene oxide)] (P(EO-r-PO)) copolymer chain, were prepared by reacting the copolymer simultaneously with α-CD and γ-CD in aqueous solution. X-ray diffraction studies demonstrated that both α-CD and γ-CD molecules in the inclusion complexes (ICs) assumed a channel-type structure. ¹H NMR spectra revealed that the compositions of the polypseudorotaxanes were strongly dependent on the molar ratio between α-CD and γ-CD in the feed. More interestingly, when we used the moderately bulk 2,4,6-trinitrophenyl (TNP) group, which is larger than the cavity of α-CD but smaller than that of γ-CD, to cap the two ends of the polypseudorotaxanes, we obtained polyrotaxanes with both α-CD and γ-CD randomly co-threaded over the P(EO-r-PO) chain, but the compositions of the polyrotaxanes were different from the corresponding polypseudorotaxanes because some γ-CD rings dethreaded since the cavity of γ-CD is larger than TNP. However, some γ-CD rings were sandwiched by α-CD rings, and these γ-CD and α-CD rings were both entrapped over the P(EO-r-PO) chain by the TNP ends. Our results revealed that how the compositions of the polypseudorotaxanes and the polyrotaxanes were different, and how their compositions were affected by the feed ratio between α-CD and γ-CD.     

Photochemistry of α,α′-Disubstituted Azoalkanes. I. Photosolvolytic Inversion and Substitution of α,α′-Dichloro- and α,α′-Dialkoyloxyazoalkanes

A series of α,α′-dichloro (α DClA), α,α′-dialkoyloxy- (αDAlA) and α,α′-dibenzoxy-azoalkanes (αDBeA) without α-aryl substituents was found to undergo meso ? dl photointerconversion upon direct irradiation through Pyrex in the presence of oxygen in a number of solvents. Furthermore, irradiation of α,α′-dipropionoxy-azoalkanes in benzene in the presence of excess acetic acid leads to substitution of the propionoxy groups by acetoxy groups in addition to meso ? dl photointerconversion. Similar irradiation in the presence of CH₃CO₂D does not lead to deuterium substitution of the β-hydrogens. The presence of benzenethiol radical scavenger does not affect the course of these photoreactions. Photosolvolysis schemes involving heterolysis (in the case of αDAlA and αDBeA) or an unstable intermediate (in the case of αDClA) are proposed.     

Copper(I)‐Catalyzed Stereoselective Synthesis of (E)‐α‐Alkynyl‐α,β‐unsaturated Esters from a Terminal Alkyne,Diazoesters and Aldehydes

A new synthetic method for α‐alkynyl‐α,β‐unsaturated esters is presented herein. The method is based on a copper(I)‐catalyzed three‐component reaction of a terminal alkyne, diazoesters and aldehydes. The reaction is featured by mild conditions, high yields and excellent stereoselectivity. Cu(I) carbene migratory insertion is proposed as the key step in the transformation.

     

Flash Spark Plasma Sintering (FSPS) of α and β SiC

A novel processing methodology that allows combined preheating and Flash‐SPS (FSPS) of silicon carbide‐based materials has been developed. Beta‐SiC (+10 wt% B₄C) powders were densified (Ф 20 mm) up to 96% of their theoretical density in 17 s under an applied pressure of 16 MPa (5 kN). The flash event was attributed to the sharp positive temperature dependence of the electrical conductivity (thermal runaway) of SiC, and a sudden increase in electric power absorption (Joule heating) of the samples after a sufficient preheating temperature (>600°C) was reached. The microstructural evolution was analyzed by examining materials densified by FSPS in the range of 82%–96% theoretical densities. FEM modeling results suggest that the FSPS heating rate was of the order of 8800°C/min. A comparative analysis was done between FSPS and reference samples (sintered using conventional SPS in the temperature range of 1800°C–2300°C). This allowed for a better understanding of the temperatures generated during FSPS, and in turn the sintering mechanisms. We also demonstrated the scalability of the FSPS process by consolidating a large α‐SiC disk (Ф 60 mm) in about 60 s inside a hybrid SPS furnace equipped with an induction heater, which allowed us to achieve sufficient preheating (1600°C) of the material to achieve FSPS.