Flame‐retardant epoxy resins: An approach from organic–inorganic hybrid nanocomposites

Phosphorus‐containing epoxy‐based epoxy–silica hybrid materials with a nanostructure were obtained from bis(3‐glycidyloxy)phenylphosphine oxide, diaminodiphenylmethane, and tetraethoxysilane in the presence of the catalyst p‐toluenesulfonic acid via an in situ sol–gel process. The silica formed on a nanometer scale in the epoxy resin was characterized with Fourier transform infrared, NMR, and scanning electron microscopy. The glass‐transition temperatures of the hybrid epoxy resins increased with the silica content. The nanometer‐scale silica showed an enhancement effect of improving the flame‐retardant properties of the epoxy resins. The phosphorus–silica synergistic effect on the limited oxygen index (LOI) enhancement was also observed with a high LOI value of 44.5. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 986–996, 2001     

Isocyanide‐Based Three‐Component Synthesis of Highly Substituted 1,6‐Dihydro‐6,6‐dimethylpyrazine‐2,3‐dicarbonitrile, 3,4‐Dihydrobenzo[g]quinoxalin‐2‐amine,and 3,4‐Dihydro‐3,3‐dimethyl‐quinoxalin‐2‐amine Derivatives

A novel and efficient isocyanide‐based multicomponent reaction between alkyl or aryl isocyanides 1 , 2,3‐diaminomaleonitrile ( 2 ), naphthalene‐2,3‐diamines ( 6 ) or benzene‐1,2‐diamine ( 9 ), and 3‐oxopentanedioic acid ( 3 ) or Meldrum's acid ( 4 ) or ketones 7 was developed for the ecologic synthesis, at room temperature under mild conditions, of 1,6‐dihydropyrazine‐2,3‐dicarbonitriles 5a – 5f in H₂O without using any catalyst, and of 3,4‐dihydrobenzo[g]quinoxalin‐2‐amine and 3,4‐dihydro‐3,3‐dimethyl‐quinoxalin‐2‐amine derivatives 8a – 8g and 10a – 10e , respectively, in the presence of a catalytic amount of p‐toluenesulfonic acid (TsOH) in EtOH, in good to excellent yields (Scheme 1).     

An Efficient Route for the Synthesis of 11‐Aroyldiindeno[1,2‐b:2′,1′‐e]pyridine‐10,12‐diones

A series of novel 11‐aroyldiindeno[1,2‐b :2′,1′‐e ]pyridine‐10,12‐dione derivatives were synthesized, in good to excellent yields and short reaction times via one‐pot, three‐component reactions between indan‐1,3‐dione, ammonium acetate, and arylglyoxal hydrates in the presence of solid p ‐toluenesulfonic acid.     

Selective Pre-concentration and Solid Phase Extraction of Mercury（Ⅱ） from Natural Water by Silica Gel-loaded （E）-N-（1-Thien-2＇-ylethylidene）-1,2-phenylenediamine Phase

Silica gel-loaded （E）-N-（1-thien-2＇-ylethylidene）-1,2-phenylenediamine （TEPDA） phase was synthesized based on physical adsorption approaches. The stability of a chemically modified TEPDA especially in concentrated hydrochloric acid that was then used as a recycling and preconcentration reagent allowed the further uses of silica gel-loaded immobilized TEPDA phase. The application of this silica gel-loaded phase to sorption of a series of metal ions was performed by using different controlling factors such as the pH of the metal ion solution and the equilibration shaking time by the static technique. This difference was interpreted on the basis of selectivity incorporated in these sulfur containing silica gel-loaded TEPDA phases. Hg（Ⅱ） was found to exhibit the highest affinity towards extraction by these silica gel-loaded TEPDA phases. The pronounced selectivity was also confirmed by the determined distribution coefficients （Kd） of all the metal ions, showing the highest value reported for mercury（Ⅱ） extraction by the silica gel immobilized TEPDA phase. The potential applications of the silica gel immobilized TEPDA phase to selective extraction of mercury（Ⅱ） from aqueous solution were successfully accomplished and preconcentration of low concentration of Hg（Ⅱ） （30 pg·mL^-1） from natural tap water with a preconcentration factor of 200 for Hg（Ⅱ） off-line analysis was conducted by cold vapor atomic absorption analysis.     

Rapid preparation of methyltrimethoxy‐modified magnetic mesoporous silica as an effective solid‐phase extraction adsorbent

A time‐saving method was applied to synthesize methyltrimethoxy‐modified magnetic mesoporous silica with or without p‐toluenesulfonic acid as the catalyst for magnetic solid‐phase extraction. The synthesized materials were systematically characterized. Results demonstrated that methyltrimethoxy modified magnetic mesoporous silica with p‐toluenesulfonic acid as the catalyst has a relatively smaller aperture and extreme hydrophobicity (water contact angle of 135°). To evaluate the feasibility of these prepared materials as effective adsorbents, it was combined with gas chromatography and electron capture detection to determine 26 polychlorinated biphenyls in environmental water. The result revealed that methyltrimethoxy modified magnetic mesoporous silica with p‐toluenesulfonic acid as the catalyst had the best extraction efficiency and recovery. Under the optimized extracted conditions, the proposed method showed good linearity within the concentration range of 5 to 200 ng/L with correlation coefficients of 0.9969 to 0.9999. The limits of detection and quantification based on signal‐to‐noise ratios of 3 and 10 were in the range of 0.16 to 0.91 and 0.52 to 3.0 ng/L, respectively. The polychlorinated biphenyl concentrations in environmental water samples were successfully determined using the developed method. PCB008 and PCB110 were 4.05 and 8.52 ng/L in Red‐Star lake water (Hubei Province, China), respectively.     

2,6‐Diaryl‐4,4‐disubstituted‐4H‐thiopyran: Source for spiro heterocycles

The 1,5‐diaryl‐3,3‐disubstituted‐1,5‐pentanedione on reaction with ammonium acetate, phosphorus pentoxide and phosphorus pentasulfide gave respective 1,4‐dihydropyridine, 4H‐pyran and 4H‐thiopyran. Novel spiro heterocycles have been obtained by the cyclocondensation of 4H‐thiopyran with hydrazine, hydroxylamine, urea and thiourea.     

One‐Pot,Three‐Component Condensation of Aldehydes, 2‐Naphthol and 1,3‐Dicarbonyl Compounds

A practical and efficient procedure for the one‐pot multicomponent couping of aryl aldehydes, 2‐naphthol and cyclic 1,3‐dicarbonyl compounds using perchloric acid adsorbed on silica gel (HClO₄‐SiO₂) as a highly efficient, inexpensive, convenient, reusable heterogeneous catalyst under solvent‐free conditions has been developed. Various biologically important 12‐aryl‐8,9,10,12‐tetrahydrobenzo[a]xanthen‐11‐one derivatives have been efficiently synthesized in high to excellent yields. The present approach offers several advantages such as shorter reaction times, simple work‐up, excellent yields, low cost, and mild reaction conditions. Furthermore, the catalyst can be recovered simply and reused without appreciable loss of its catalytic activity.     

Synthesis of 2‐Aryl‐1‐arylmethyl‐1H‐1,3‐benzimidazole Derivatives Using Silica‐bonded Propyl‐S‐sulfonic Acid as Recyclable Solid Acid Catalyst

A highly selective synthesis of 2‐aryl‐1‐arylmethyl‐1H‐1,3‐benzimidazoles from the reaction of o‐phenylenediamine and aromatic aldehydes in the presence of silica‐bonded propyl‐S‐sulfonic acid (SBSSA) at 80°C in water in good to excellent yields was developed.     

Synthesis of 7‐acetyloxy‐3,7‐dimethy1‐7,8‐dihydro‐6H‐isochromene‐6,8‐dione and its analogues

7‐Alkanoyloxy‐3,7‐dimefhyl‐7,8‐dihydro‐6H‐isochromene‐6,8‐diones 12‐15 were synthesized in 69‐16% yields from the reaction of 2,4‐dihydroxy‐3‐methyl‐6‐(2‐oxopropyl)benzaldehyde 11 with p‐toluenesulfonic acid in various carboxylic acids such as acetic acid, propionic acid, butyric acid and heptanoic acid followed by oxidation with lead tetraacetate. On the other hand, (±)‐daldinin A 5 (oleate) was not obtained using oleic acid as a medium. In the cases of heptanoic acid and oleic acid, esters 16 and 17 were produced in 23 and 9% yields, respectively. 6,8‐Dihydroxy‐3,7‐dimethyl‐2‐benzopyrylium p‐toluenesulfonate 31 is considered as the intermediate for the production of 12‐15. Overall yields of isochromenes 12‐15 were 26‐6% starting from 2‐methylresorcinol for seven steps.     

A One‐pot Facile Synthesis of 2,3‐Dihydroxyquinoxaline and 2,3‐Dichloroquinoxaline Derivatives Using Silica Gel as an Efficient Catalyst

An efficient one‐pot reaction has been developed for the synthesis of 2,3‐dichloroquinoxaline derivatives 3a – n . The reaction was performed in two steps via a silica gel catalyzed tandem process from o‐phenylenediamine and oxalic acid, followed by addition of phosphorus oxychloride (POCl₃). A variety of 2,3‐dichloroquinoxalines have been obtained in good to excellent overall yields. Eight known compounds 3a – 3h were characterized by IR, ¹H‐NMR, and mass spectroscopies. Compounds 3i – 3n without spectroscopic data were characterized by IR, ¹H‐NMR, ¹³C‐NMR, and mass spectroscopies.     

Synthesis of high‐performance polyurethanes with rigid 5‐6‐5‐fused ring system in the main chain from naturally occurring myo‐inositol

A bisketal of myo‐inositol was used as a diol‐type monomer for synthesis of polyurethanes. The monomer was obtained by treatment of myo‐inositol with 1,1‐dimethoxycyclohexane in the presence of p‐toluenesulfonic acid as a catalyst. The ketalization resulted in the formation of a 5‐6‐5‐fused ring system, which endowed the diol‐type monomer with high rigidity. The diol readily reacted with diisocyanate to give the corresponding polyurethane, which exhibited excellent heat resistance due to the rigid 5‐6‐5 system in the main chain. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3956–3963     

Magnetic Nanoparticle Supported Ionic Liquid Assisted Green Synthesis of Pyrazolopyranopyrimidines and 1,6‐diamino‐2‐oxo‐1,2,3,4‐tetrahydropyridine‐3,5‐ dicarbonitriles

A simple and eco‐friendly green protocol was used for synthesis of pyrazolopyranopyrimidines via four‐component reaction of hydrazine hydrate, ethyl acetoacetate, barbituric acid or dimethyl barbituric acid, and aromatic aldehydes under thermal and solvent‐free conditions in the presence of magnetic nanoparticle supported silica bonded n‐propyl‐4‐aza‐1‐azoniabicyclo[2.2.2]octane chloride (MNPs@DABCO⁺Cl^?) as an efficient, recyclable heterogeneous catalyst. MNPs@DABCO⁺Cl^? also catalyzed the synthesis of 1,6‐diamino‐2‐oxo‐1,2,3,4‐tetrahydropyridine‐3,5‐dicarbonitrile derivatives by four‐component reaction of hydrazine hydrate, malononitrile, ethyl cyanoacetate and ketones under thermal and solvent‐free conditions at 80 °C. These methods are practical and offer many advantages, such as high yields, short reaction times, and simple work‐up.     

Silica Gel‐Supported Polyphosphoric Acid (PPA/SiO2): An Efficient and Reusable Heterogeneous Catalyst for Facile Synthesis of 14‐Aryl‐14H‐dibenzo[a,j]xanthenes under Solvent‐free Conditions

A simple, efficient and green method for the synthesis of 14‐aryl‐14H‐dibenzo[a,j]xanthenes by a one‐pot condensation reaction of β‐naphthol and aryl aldehydes using silica gel‐supported polyphosphoric acid (PPA/SiO₂), an effective and reusable catalyst, under solvent‐free conditions is described. The present methodology offers several advantages, such as a simple procedure with an easy work‐up, short reaction times, high yields, and the absence of any volatile and hazardous organic solvents.     

Synthesis of 1‐Methyl‐6,10‐diphenylheptalene Derivatives

The reduction of heptalene diester 1 with diisobutylaluminium hydride (DIBAH) in THF gave a mixture of heptalene‐1,2‐dimethanol 2a and its double‐bond‐shift (DBS) isomer 2b (Scheme 3). Both products can be isolated by column chromatography on silica gel. The subsequent chlorination of 2a or 2b with PCl₅ in CH₂Cl₂ led to a mixture of 1,2‐bis(chloromethyl)heptalene 3a and its DBS isomer 3b . After a prolonged chromatographic separation, both products 3a and 3b were obtained in pure form. They crystallized smoothly from hexane/Et₂O 7 : 1 at low temperature, and their structures were determined by X‐ray crystal‐structure analysis (Figs. 1 and 2). The nucleophilic exchange of the Cl substituents of 3a or 3b by diphenylphosphino groups was easily achieved with excess of (diphenylphospino)lithium (=lithium diphenylphosphanide) in THF at 0° (Scheme 4). However, the purification of 4a / 4b was very difficult since these bis‐phosphines decomposed on column chromatography on silica gel and were converted mostly by oxidation by air to bis(phosphine oxides) 5a and 5b . Both 5a and 5b were also obtained in pure form by reaction of 3a or 3b with (diphenylphosphinyl)lithium (=lithium oxidodiphenylphospanide) in THF, followed by column chromatography on silica gel with Et₂O. Carboxaldehydes 7a and 7b were synthesized by a disproportionation reaction of the dimethanol mixture 2a / 2b with catalytic amounts of TsOH. The subsequent decarbonylation of both carboxaldehydes with tris(triphenylphosphine)rhodium(1+) chloride yielded heptalene 8 in a quantitative yield. The reaction of a thermal‐equilibrium mixture 3a / 3b with the borane adduct of (diphenylphosphino)lithium in THF at 0° gave 6a and 6b in yields of 5 and 15%, respectively (Scheme 4). However, heating 6a or 6b in the presence of 1,4‐diazabicyclo[2.2.2]octane (DABCO) in toluene, generated both bis‐phosphine 4a and its DBS isomer 4b which could not be separated. The attempt at a conversion of 3a or 3b into bis‐phosphines 4a or 4b by treatment with t‐BuLi and Ph₂PCl also failed completely. Thus, we returned to investigate the antipodes of the dimethanols 2a, 2b , and of 8 that can be separated on an HPLC Chiralcel‐OD column. The CD spectra of optically pure (M)‐ and (P)‐configurated heptalenes 2a, 2b , and 8 were measured (Figs. 4, 5, and 9).     

The Convenient Synthesis of 11‐Methyl‐3,8‐disubstituted‐12‐aryl‐3,4,7,8,9,12‐hexahydro‐1H‐chromeno[2,3‐b]quinoline‐1,10(2H)‐dione Derivatives

The 2‐arylidene‐3‐oxobutanenitrile derivatives 2 were prepared by the Knoevenagel condensation between aldehydes and 3‐oxobutanenitrile 1 , which was obtained by acid hydrolysis of β‐aminocrotononitrile. 3‐Acetyl‐2‐amino‐4H‐chromen‐5(6H)‐one derivatives 3 were synthesized by reaction of 2‐arylidene‐3‐oxobutanenitrile 2 and 5‐substituted‐1,3‐cyclohexanedione in ethylene glycol. The 11‐methyl‐3,8‐disubstituted‐12‐aryl‐3,4,7,8,9,12‐hexahydro‐1H‐chromeno[2,3‐b]quinoline‐1,10(2H)‐dione derivatives 4 were obtained by Friedländer reaction of compounds 3 with 5‐substituted‐1,3‐cyclohexanedione, using p‐toluenesulfonic acid monohydrate as catalyst. The structures of all novel compounds were characterized by elemental analysis, IR, MS, and ¹H NMR spectra. The crystal and molecular structure of compound 4f has been determined by single crystal XRD analysis.     

Semiconducting polymers from triphenylamine derivatives‐benzaldehyde polymers by oxidization with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ)

4‐Tolyldiphenylamine (TDPA) and N,N′‐diphenyl‐N,N′‐bis(4‐methylphenyl)‐1,1′‐biphenyl‐4,4′‐diamine (TPD), were reacted with benzaldehyde (BA) using p‐toluenesulfonic acid as a catalyst to yield linear polymers. The polymers were reacted with 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) in tetrahydrofuran (THF) at room temperature. ¹H‐NMR showed that all the methine protons in the residue of BA were completely removed at the mole ratio of repeating unit : DDQ, 2 : 1. The resulting polymers showed good solubility in chloroform or THF. The reacted TDPA‐BA and TPD‐BA polymers gave new UV absorption peaks at 697.0 and 722.5 nm and showed reversible redox potentials about 0.994 and 1.021 V, respectively. Direct current (d.c.) conductivity of the reacted polymers was in the range of 10^?11 S/cm, which is more than two orders higher than the unreacted polymers. The polymer showed pentad split electron spin resonance (ESR) signal, whose concentration was one in 670 or 230 repeating unit for TDPA‐BA and TPD‐BA polymers, respectively. Copyright © 2001 John Wiley & Sons, Ltd.     

A Facile Synthesis of 2‐Substituted 2,3‐Dihydro‐4(1H)‐Azuleno[2,1‐d]Pyrimidinones

A facile, efficient, and novel approach to access 2‐substituted 2,3‐dihydro‐4(1H)‐azuleno[2,1‐d]pyrimidinones was developed by condensation of 2‐amino‐1‐carbamoyl‐3‐phenylazulene with ary1 aldehydes or ketones in ionic liquids by catalyzed p‐toluenesulfonic acid.     

Silica‐gel‐supported Phosphorus Pentoxide:a Simple and Efficient Solid‐supported Reagent for Esterification of Long‐ Chain Carboxylic Acids and Their Antimicrobial Screening

A silica-gel-supported heterogeneous phosphorus pentoxide reagent has been developed for the esterification of various long-chain carboxylic acids with aromatic alcohols. The reactions occurred under relatively mild conditions and afforded the desired products in good yields. All the compounds 3a—3x were screened for antibacterial and antifungal activity, which showed good activity against Gram positive and Gram negative bacteria and also good results against almost all fungal strains. The structures of the synthesized compounds were elucidated by IR, ¹H NMR, ¹³C NMR, mass spectroscopic techniques and elemental analysis.     

An Efficient Synthesis of Benzo[g]thiazolo[2,3‐b]quinazolin‐4‐ium and Benzo[g]benzo[4,5]thiazolo[2,3‐b]quinazolin‐14‐ium Hydroxides by a One‐pot,Three‐component Reaction under Green Conditions

A new series of benzo[g]thiazolo[2,3‐b]quinazolin‐4‐ium and benzo[g]benzo[4,5]thiazolo[2,3‐b]quinazolin‐14‐ium hydroxide derivatives have been synthesized by the one‐pot, three‐component reaction of aryl glyoxal monohydrates, 2‐hydroxy‐1,4‐naphthoquinone, and 2‐aminothiazole or 2‐aminobenzothiazole in the presence of triethylamine and p‐toluenesulfonic acid as organocatalysts in H₂O/acetone (2:1) at room temperature. This method offers mild reaction conditions, excellent yields, easy workup, and readily accessible starting materials and catalysts.     

A Convenient Method for the Preparation of 1,5‐Diaryl‐3‐(arylamino)‐1H‐pyrrol‐2(5H)‐ones

A simple and eco‐friendly method for the preparation of 1,5‐diaryl‐3‐(arylamino)‐1H‐pyrrol‐2(5H)‐ones via the cyclo‐condensation reaction of aldehydes, amines and ethyl pyruvate in the presence of silica supported ferric chloride (SiO₂‐FeCl₃) as reusable heterogeneous catalyst is described. The present methodology offers several advantages such as excellent yields, simple procedure and short reaction times.