Epoxy resins from novel monomers with a bis‐(9,10‐dihydro‐9‐oxa‐10‐oxide‐10‐phosphaphenanthrene‐10‐yl‐) substituent

A new diepoxide and a new diamine, both bearing bis‐(9,10‐dihydro‐9‐oxa‐10‐oxide‐10‐phosphaphenanthrene‐10‐yl‐)‐substituted methylene linkages, were prepared through the reaction of 9,10‐dihydro‐oxa‐10‐phosphaphenanthrene‐10‐oxide with benzophenone derivatives via a simple addition reaction followed by a dehydration reaction. These two compounds were used as monomers for preparing cured epoxy resins with high phosphorus contents. The resultant epoxy resins showed high glass‐transition temperatures (between 131 and 196 °C). All of the cured epoxy resins exhibited high thermal stability, with 5% weight loss temperatures over 316 °C, and excellent flame retardancy, with limited oxygen index values of 37–50. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 359–368, 2002     

Deep‐Eutectic‐Solvent‐Based Self‐Healing Polymer Electrolyte for Safe and Long‐Life Lithium‐Metal Batteries

The deployment of high‐energy‐density lithium‐metal batteries has been greatly impeded by Li dendrite growth and safety concerns originating from flammable liquid electrolytes. Herein, we report a stable quasi‐solid‐state Li metal battery with a deep eutectic solvent (DES)‐based self‐healing polymer (DSP) electrolyte. This electrolyte was fabricated in a facile manner by in situ copolymerization of 2‐(3‐(6‐methyl‐4‐oxo‐1,4‐dihydropyrimidin‐2‐yl)ureido)ethyl methacrylate (UPyMA) and pentaerythritol tetraacrylate (PETEA) monomers in a DES‐based electrolyte containing fluoroethylene carbonate (FEC) as an additive. The well‐designed DSP electrolyte simultaneously possesses non‐flammability, high ionic conductivity and electrochemical stability, and dendrite‐free Li plating. When applied in Li metal batteries with a LiMn₂O₄ cathode, the DSP electrolyte effectively suppressed manganese dissolution from the cathode and enabled high‐capacity and a long lifespan at room and elevated temperatures.     

An Efficient One‐pot Synthesis of Aryl‐substituted 1‐(Thiazol‐2‐yl)‐1H‐pyrazole‐3‐carboxylates via a Hantzsch Synthesis‐Knorr Reaction Sequence

The treatment of α‐bromoalkyl aryl ketones and 2‐(propan‐2‐ylidene)hydrazine carbothioamide afforded 4‐aryl‐2‐(2‐(propan‐2‐ylidene)hydrazinyl)thiazoles via a Hantzsch‐thiazole synthesis, which reacted with 4‐aryl‐2,4‐diketoesters via a sequential Knorr‐pyrazole reaction to deliver a variety of aryl‐substituted ethyl 1‐(thiazol‐2‐yl)‐1H‐pyrazole‐3‐carboxylates in a one‐pot fashion with moderate to high yields. The key intermediates 4‐aryl‐2,4‐diketoesters, existing as its enolic lithium salt, were synthesized in situ by a high‐yield tert‐BuOLi‐mediated Claisen condensation of alkylphenones and diethyl oxalate. This class of elegant molecule comprises aryl groups on the two different heterocyclic cores, and the configurations of two representative molecules were determined by single crystal X‐ray crystallography.     

Synthesis,Characterization, and Energetic Properties of 6‐Amino‐tetrazolo[1,5‐b]‐1,2,4,5‐tetrazine‐7‐N‐oxide: A Nitrogen‐Rich Material with High Density

The synthesis and energetic properties of a novel N‐oxide high‐nitrogen compound, 6‐amino‐tetrazolo[1,5‐b]‐1,2,4,5‐tetrazine‐7‐N‐oxide, are described. Resulting from the N‐oxide and fused rings system, this molecule exhibits high density, excellent detonation properties, and acceptable impact and friction sensitivities, which suggests potential applications as an energetic material. Compared to known high‐nitrogen compounds, such as 3,6‐diazido‐1,2,4,5‐tetrazine (DiAT), 2,4,6‐tri(azido)‐1,3,5‐triazine (TAT), and 4,4′,6,6′‐tetra(azido)azo‐1,3,5‐triazine (TAAT), a marked performance and stability increase is seen. This supports the superior qualities of this new compound and the advantage of design strategy.     

Shapeable matrix‐free Spectra® fiber‐reinforced polymeric composites via high‐temperature high‐pressure sintering: Process‐structure‐property relationship

In an exploratory effort to find a new way to make high‐performance composites used in ballistic protective applications, matrix‐free Spectra® fiber‐reinforced polymeric composites are produced via a novel processing method called high‐temperature high‐pressure sintering. Mechanical testing at ambient and elevated temperatures proves that the fibers can maintain their properties after processing. The characteristics and properties of the final products vary with different processing conditions. Their microstructure and morphology were investigated using SEM and WAXD. Their mechanical properties, including interlayer adhesion, rigidity, and ballistic performance, were measured and compared with those of the conventional composites. The sintering mechanism is proposed and verified. Spectra cloth is capable of being shaped to produce complex double curvatures by a thermoforming process, using a simple hemispherical mold. Success in different molding sequences and procedures shows the versatility in manufacturing. The theoretical background for the thermoformability is explained in terms of molecular interaction, microstructure, and morphology. Selective thermomechanical properties of the molded structures were measured. By combining the knowledge and information from the aforementioned studies, the process‐structure‐property relationship is established, which gives in‐depth and better understanding of this unique high‐temperature high‐pressure sintering process for consolidating Spectra cloth. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2767–2789, 2005     

Microwave‐induced Stereoselectivity in Synthesis of trans‐4‐Aryl‐3‐methyl‐6‐oxo‐4,5,6,7‐tetrahydro‐2H‐pyrazolo[3,4‐b]pyridine‐5‐carbonitriles

A facile synthesis of trans isomers of 4‐aryl‐3‐methyl‐6‐oxo‐4,5,6,7‐tetrahydro ‐ 2H ‐ pyrazolo[3,4‐b]pyridine‐5‐carbonitriles via three‐component condensation reaction of an aldehyde, 3‐amino‐5‐methylpyrazole and ethyl cyanoacetate in acetonitrile has been developed under microwave irradiation. This one‐pot reaction proceeds without any catalyst in short times and gives the product in high selectivities and high yields.     

9,9‐Diaryl‐4,5‐diazafluorene‐based Cardo polymer; Synthesis and characteristic properties

To open out new aspects of 9,9‐diarylfluorene (DAF)‐based polymers with high performances, 9,9‐(4‐hydroxyphenyl)‐4,5‐diazafluorene ( N‐BPF ) was designed as a new cardo structure and the properties of poly(ether ketone)s ( N‐PEKs ) containing N‐BPF skeletons were examined in detail. N‐PEKs were synthesized in high yields via polycondensation of N‐BPF with difluoroarenes. N‐PEKs showed cardo polymer‐specific properties such as high thermal stability and high solubility in organic solvents. The addition of p‐toluenesulfonic acid (TsOH) to N‐PEK resulted in the formation of network polymer based on interchain hydrogen bonds. It turned out that the films of network polymer are flexible and transparent and exhibit high refractive index and low birefringence. The effects of feed ratio of TsOH to N‐PEK were also evaluated on the mechanical properties of network polymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4541–4549     

An Efficient Synthesis of 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐6‐methyl‐4‐(2‐oxo‐2‐phenylethoxy)‐3,4‐dihydro‐2H‐pyran‐2‐one Derivatives via Multi‐Component Approach

An easy, highly efficient and a new convenient one‐pot, two‐step approach to the synthesis of 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐6‐methyl‐4‐(2‐oxo‐2‐phenylethoxy)‐3,4‐dihydro‐2H‐pyran‐2‐one is described. These compounds were synthesized from 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐4‐hydroxy‐6‐methyl‐3,4‐dihydro‐2H‐pyran‐2‐one and α‐bromoketones in good yields. The compounds 4 were synthesized by a multi‐component reaction between 1 , 2 , and 3 and the prominent features of this protocol are mild reaction conditions, operation simplicity, and good to high yields of products.     

An Efficient and Facile Synthesis of 5‐Amino‐3‐methyl‐7‐aryl‐1,3‐dihydroisobenzofuran‐4,6‐dicarbonitrile Derivatives Under Mild Conditions

This article describes an efficient approach for the synthesis of 5‐amino‐3‐methyl‐7‐aryl‐1,3‐dihydroisobenzofuran‐4,6‐dicarbonitrile derivatives from the reaction of aromatic aldehyde, 2‐methyltetrahydrofuran‐3‐one, and malononitrile under mild conditions. This is a simple and facile process to structure this important heterocyclic compounds. The other advantages of this approach are rapid reaction rate, high yield, and simple procedure. This article provided a good method for the synthesis of 1,3‐dihydroisobenzofuran derivatives.     

Ultra‐high‐pressure‐assisted extraction of wedelolactone and isodemethylwedelolactone from Ecliptae Herba and purification by high‐speed counter‐current chromatography

Ultra‐high‐pressure extraction combined with high‐speed counter‐current chromatography was employed to extract and purify wedelolactone and isodemethylwedelolactone from Ecliptae Herba. The operating conditions of ultra‐high‐pressure extraction were optimized using an orthogonal experimental design. The optimal conditions were 80% aqueous methanol solvent, 200 MPa pressure, 3 min extraction time and 1:20 (g/mL) solid–liquid ratio for extraction of wedelolactone and isodemethylwedelolactone. After extraction by ultra‐high pressure, the extraction solution was concentrated and subsequently extracted with ethyl acetate; a total of 2.1 g of crude sample was obtained from 100 g of Ecliptae Herba. A two‐phase solvent system composed of petroleum ether–ethyl acetate–methanol–water (3:7:5:5, v/v) was used for high‐speed counter‐current chromatography separation, by which 23.5 mg wedelolactone, 6.8 mg isodemethylwedelolactone and 5.5 mg luteolin with purities >95% were purified from 300 mg crude sample in a one‐step separation. This research demonstrated that ultra‐high‐pressure extraction combined with high‐speed counter‐current chromatography was an efficient technique for the extraction and purification of coumestans from plant material.     

Construction of a High‐Mannose‐Type Glycan Library by a Renewed Top‐Down Chemo‐Enzymatic Approach

A comprehensive method for the construction of a high‐mannose‐type glycan library by systematic chemo‐enzymatic trimming of a single Man9‐based precursor was developed. It consists of the chemical synthesis of a non‐natural tridecasaccharide precursor, the orthogonal demasking of the non‐reducing ends, and trimming by glycosidases, which enabled a comprehensive synthesis of high‐mannose‐type glycans in their mono‐ or non‐glucosylated forms. It employed glucose, isopropylidene, and N‐acetylglucosamine groups for blocking the A‐, B‐, and C‐arms, respectively. After systematic trimming of the precursor, thirty‐seven high‐mannose‐type glycans were obtained. The power of the methodology was demonstrated by the enzymatic activity of human recombinant N‐acetylglucosaminyltransferase‐I toward M7–M3 glycans, clarifying the substrate specificity in the context of high‐mannose‐type glycans.     

SiO2 Nanoparticle‐catalyzed Facile and Efficient One‐pot Synthesis of N‐alkyl‐2,5‐bis[(E)‐2‐phenylvinyl]‐1,3‐dioxol‐4‐amine Under Solvent‐free Conditions

1,3‐Dioxole‐4‐amine derivatives have been prepared efficiently in one‐pot reaction using nanosized SiO₂ as a heterogeneous catalyst. The present method does not involve any hazardous organic solvents or catalysts. The high surface‐to‐volume ratio of SiO₂ nanoparticle has promising features for the reaction response such as the short reaction time, good to excellent yields, easy of operation and work‐up procedure, and purification of products by non‐chromatographic methods.     

Facile synthesis of model 1,4‐dihydro‐1H‐1,3,4‐benzotriazepin‐5‐ones

2‐Aminobenzoic acid reacts readily, in the presence of triethylamine, with hydrazonoyl chlorides ( 5a‐c ) (precursors of the reactive nitrile imine 1,3‐dipolar species) to afford high yields of the corresponding acyclic amidrazone adducts ( 6a‐c ). The latter adducts undergo, in THF in presence of 1,1‐carbonyldiimida‐zole, smooth intramolecular cyclization involving the activated carboxyl and the NH‐ termini to deliver unequivocally the respective dihydro‐1,3,4‐benzotriazepin‐5‐ones ( 7a‐c ).     

Multi‐Gram Scale Synthesis of Chiral 3‐Methyl‐2,5‐trans‐tetrahydrofurans

In this article, we report the rapid and facile synthesis of chiral 3‐methyl‐2,5‐trans‐tetrahydrofurans. This reaction utilizes cheap and easily available starting materials. A domino hydrolysis and intramolecular Michael‐type ring closure reaction was the key step. As a result, synthesis of the desired 3‐methyl‐2,5‐trans‐tetrahydrofurans could be achieved in gram‐scale over seven linear steps with high chemical yield and high diastereoselectivity.     

Synthesis and characterization of a series of 1,x‐bis‐(4‐oxo‐3,4‐dihydro‐1,2,3‐benzotriazin‐3‐yl)alkanes

Reaction of isatoic anhydride with an alkanediamine in DMF solution under mild conditions affords excellent yields of the 1,x‐bis‐{(2‐aminobenzoyl‐)amino}alkanes ( 2a‐k ), which have been characterized by IR and NMR spectroscopy, high resolution mass spectrometry and elemental analysis. Diazotization of the bis‐{(2‐aminobenzoyl‐)‐amino}alkanes in aqueous solution gives high yields of the 1,x‐bis‐(4‐oxo‐3,4‐dihydro‐1,2,3‐benzotriazin‐3‐yl)alkanes ( 1a‐k ), whch have also been characterized by IR and NMR spectroscopy, high resolution mass spectrometry and elemental analysis. The alkanediamines employed are as follows: ethylene diamine, 1,3‐propanediamine, 1,2‐propanediamine, 2‐methyl‐1,2‐propanediamine, 2,2‐dimethyl‐1,3‐propanediamine, 2‐hydroxy‐1,3‐propanediamine, 1,4‐diaminobutane, 1,5‐diaminopentane, 1,3‐diaminopentane (DYTEK® EP diamine), 1,6‐diaminohexane and 1,7‐diaminoheptane. The alternative method of synthesis of the bis‐(4‐oxo‐3,4‐dihydro‐1,2,3‐benzotriazin‐3‐yl)alkanes ( 1 ) via the diazonium salt from methyl anthranilate was explored.     

1，3—Diphenyl—5—（9—phenanthry1）—2—pyrazoline（DPPhP）：An Excellent Ho1e—Transport Material for Use in Organic Light—Emitting Diodes

An excellent hole-transport material,1,3-diphenyl-5-(9-phenanthryl)-2-pyrazoline(DPPhP)for OLEDs was studied.This compound not only offers hlgh glass transition temperature(Tg=96℃）,good film forming ability,and high HOMO energy level,but also displays excellent hole-transport property.The electrlumlnescent device with a simple structure of ITO/DPPhP(60nm)/AIQ(60mm)/LiF(0.8nm)/Al shows an external quantom efficiency as high as 1.6?     

One‐Pot Three‐Component Mild Synthesis of 2‐Aryl‐3‐(9‐alkylcarbazol‐3‐yl)thiazolidin‐4‐ones

A series of novel 2‐aryl‐3‐(9‐alkylcarbazol‐3‐yl)thiazolidin‐4‐ones were synthesized by one‐pot three‐component reactions of 3‐amino‐9‐alkylcarbazoles, aromatic aldehydes, and 2‐mercaptoacetic acid by using dicyclohexylcarbodiimide (DCC) as a cyclizing agent in dry diethyl ether at room temperature. This protocol has advantages of mild condition, short reaction time, high yield, and simple work‐up procedure.     

An Adjustable‐Porosity Plastic Crystal Electrolyte Enables High‐Performance All‐Solid‐State Lithium‐Oxygen Batteries

The limited triple‐phase boundaries (TPBs) in solid‐state cathodes (SSCs) and high resistance imposed by solid electrolytes (SEs) make the achievement of high‐performance all‐solid‐state lithium‐oxygen (ASS Li‐O₂) batteries a challenge. Herein, an adjustable‐porosity plastic crystal electrolyte (PCE) has been fabricated by employing a thermally induced phase separation (TIPS) technique to overcome the above tricky issues. The SSC produced through the in‐situ introduction of the porous PCE on the surface of the active material, facilitates the simultaneous transfer of Li⁺/e^?, as well as ensures fast flow of O₂, forming continuous and abundant TPBs. The high Li⁺ conductivity, softness, and adhesion of the dense PCE significantly reduce the battery resistance to 115 Ω. As a result, the ASS Li‐O₂ battery based on this adjustable‐porosity PCE exhibits superior performances with high specific capacity (5963 mAh g^?1), good rate capability, and stable cycling life up to 130 cycles at 32 °C. This novel design and exciting results could open a new avenue for ASS Li‐O₂ batteries.     

Reactivity of 2‐Methyl‐4H‐3,1‐benzoxazin‐4‐ones and 2‐Methyl‐4H‐pyrido[2,3‐d][1,3]oxazin‐4‐one under Microwave Irradiation Conditions

The reactivity of variably substituted 2‐methyl‐4H‐3,1‐benzoxazin‐4‐ones and 2‐methyl‐4H‐pyrido[2,3‐d][1,3]oxazin‐4‐one towards carbon and oxygen nucleophiles under microwave irradiation conditions was investigated. Optimization of the reaction conditions of oxazinones with carbon nucleophiles led to the synthesis of a series of 4‐hydroxy‐quinolin‐2‐ones and 4‐hydroxy‐1,8‐naphthyridin‐2‐ones in high yields, whereas reaction with a variety of alcohols proceeded smoothly to the formation of the corresponding N‐acetyl‐anthranilates and nicotinates.     

A Novel Bat‐Shaped Dicyanomethylene‐4H‐pyran‐Functionalized Naphthalimide for Highly Efficient Solution‐Processed Multilevel Memory Devices

Small‐molecule‐based multilevel memory devices have attracted increasing attention because of their advantages, such as super‐high storage density, fast reading speed, light weight, low energy consumption, and shock resistance. However, the fabrication of small‐molecule‐based devices always requires expensive vacuum‐deposition techniques or high temperatures for spin‐coating. Herein, through rational tailoring of a previous molecule, DPCNCANA (4,4′‐(6,6′‐bis(2‐octyl‐1,3‐dioxo‐2,3‐dihydro‐1H‐benzo[de]isoquinolin‐6‐yl)‐9H,9′H‐[3,3′‐bicarbazole]‐9,9′‐diyl)dibenzonitrile), a novel bat‐shaped A‐D‐A‐type (A‐D‐A=acceptor–donor–acceptor) symmetric framework has been successfully synthesized and can be dissolved in common solvents at room temperature. Additionally, it has a low‐energy bandgap and dense intramolecular stacking in the film state. The solution‐processed memory devices exhibited high‐performance nonvolatile multilevel data‐storage properties with low switching threshold voltages of about −1.3 and −2.7 V, which is beneficial for low power consumption. Our result should prompt the study of highly efficient solution‐processed multilevel memory devices in the field of organic electronics.