An Efficient synthesis of pyrimido[4,5‐b]quinoline and indeno[2′,1′:5,6]pyrido[2,3‐d]pyrimidine derivatives via multicomponent reactions in ionic liquid

A series of pyrimido[4,5‐b]quinoline and indeno[2′,1′:5,6]pyrido[2,3‐d]pyrimidine derivatives were synthesized via the three‐component reaction of an aldehyde, 6‐aminopyrimidine‐2,4‐dione and 5,5‐dimethyl‐1,3‐cyclohexanedione or 1,3‐indanedione in ionic liquid 1‐n‐butyl‐3‐methylimidazolium bromide ([bmim]Br). This protocol has the advantages of easier work‐up, milder reaction conditions, high yields and an environmentally benign procedure compared with other methods.     

Oxidation-Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2O2

The full reaction photosynthesis of H₂O₂ that can combine water-oxidation and oxygen-reduction without sacrificial agents is highly demanded to maximize the light-utilization and overcome the complex reaction-process of anthraquinone-oxidation. Here, a kind of oxidation-reduction molecular junction covalent-organic-framework (TTF-BT-COF) has been synthesized through the covalent-coupling of tetrathiafulvalene (photo-oxidation site) and benzothiazole (photo-reduction site), which presents visible-light-adsorption region, effective electron-hole separation-efficiency and photo-redox sites that enables full reaction generation of H₂O₂. Specifically, a record-high yield (TTF-BT-COF, ≈276 000 μM h⁻¹ g⁻¹) for H₂O₂ photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation-reduction molecular junction COFs for full reaction photosynthesis of H₂O₂, which might extend the scope of COFs in H₂O₂ production.     

Preparation and characterization of cellulose acetate‐coated compound fertilizer with controlled‐release and water‐retention

A novel cellulose acetate‐coated compound fertilizer with controlled‐release and water‐retention (CAFCW) was prepared, which possessed the three‐layer structure. Its core was water‐soluble compound fertilizer granular, the inner coating was cellulose acetate (CA), and the outer coating was poly(acrylic acid‐co‐acrylamide)/unexpanded vermiculite (P(AA‐co‐AM)/UVMT) superabsorbent composite. The effects of the amount of acrylamide, crosslinker, initiator, degree of neutralization of acrylic acid (AA), and unexpanded vermiculite concentration on water absorbency were investigated and optimized. The water absorbency of CAFCW was 72 times its own weight if it was allowed to swell in tap water at room temperature for 90 min. Element analysis and atomic absorption spectrophotometer results showed that the product contained 11% nitrogen, 6% phosphorus (shown by P₂O₅), 9% potassium (shown by K₂O), 1% calcium (shown by CaO), and 0.4% magnesium (shown by MgO). Swelling rate, slow‐release, and water‐retention properties of CAFCW were also investigated. This product with good controlled‐release and water‐retention capacity, being degradable in soil and environmentally friendly, could be especially useful in agricultural and horticultural applications. Copyright © 2008 John Wiley & Sons, Ltd.     

Electroreduction Enables Regioselective 1,2-Diarylation of Alkenes with Two Electrophiles

Precisely introducing two similar functional groups into bulk chemical alkenes represents a formidable route to complex molecules. Especially, the selective activation of two electrophiles is in crucial demand, yet challenging for cross-electrophile-coupling. Herein, we demonstrate a redox-mediated electrolysis, in which aryl nitriles are both aryl radical precursors and redox-mediators, enables an intermolecular alkene 1,2-diarylation with a remarkable regioselectivity, thereby avoiding the involvement of transition-metal catalysts. This transformation utilizes cyanoarene radical anions for activating various aryl halides (including iodides, bromides, and even chlorides) and affords 1,2-diarylation adducts in up to 83 % yield and >20 : 1 regioselectivity with more than 80 examples, providing a feasible approach to complex bibenzyl derivatives.     

A new strategy for designing non-C2-symmetric monometallic bifunctional catalysts and their application in enantioselective cyanation of aldehydes

A monometallic bifunctional catalyst, in which only one imidazolyl moiety is directly attached at the 3-position of a binaphthol moiety, has been developed. The ligand (R)-1, which lacks C2-symmetry and flexible linkers, in combination with Ti(OiPr)4, has been demonstrated to promote the enantioselective cyanation of aldehydes with trimethylsilylcyanide (TMSCN), giving excellent enantioselectivities of up to 98 % ee and high yields of up to 99 %. The use of this bifunctional catalytic system obviates the need for additives and is extremely simple as the reagents are added in one portion at the beginning of the reaction. The protocol has been found to tolerate a relatively wide range of aldehydes when 10 mol % of the (R)-1/Ti(OiPr)4 complex is deployed in CH2Cl2 at -40 degrees C, the conditions which proved most practical and effective. The asymmetric cyanations also proceeded with lower catalyst loadings (5 mol %, or even 2 mol %), still giving satisfactory enantiomeric excesses and yields. Interestingly, the use of freshly distilled TMSCN dried over CaH2 gave a low enantioselectivity and only a moderate yield of the adduct as compared with direct use of the commercial reagent. The results of 13C NMR spectroscopic studies implicate HCN as the actual reactive nucleophile.     

Syntheses and Preliminary Biological Evaluations of the Dibromopyrrole-Containing Marine Natural Products Agesasine A,Agesasine B,Longamide E and Various Congeners

Total syntheses of the title marine natural products have been achieved and so confirming the structures originally assigned to them. Upon subjecting agesasine A and its corresponding ethyl ester to Mitsunobu conditions, a 1,5-cyclodehydration reaction takes place to give 2-oxazolines. In contrast, on subjecting agesasine B to the same Mitsunobu conditions, a simple dehydration reaction occurs to give the corresponding acrylate. A total synthesis of longamide E was achieved by engaging a 1,2-disubstituted pyrrole in a lactam-forming reaction and this was followed by a two-fold and fully regio-controlled bromination reaction. A distinctly different and possibly biomimetic route was used to synthesize, via the open-chain natural product nakamurine B, longamide B and its methyl ester. Preliminary biological evaluations of the title alkaloids and various analogues against a small human cancer cell line panel reveals cytotoxic properties that vary significantly with structure.     

Hyperfine interactions in nanocrystallized NANOPERM-type metallic glass containing Mo

NANOPERM-type alloy with chemical composition Fe₇₆Mo₈CuB₁₅ was studied by combination of ⁵⁷Fe Mössbauer spectroscopy and ⁵⁷Fe(¹⁰B, ¹¹B) nuclear magnetic resonance in order to determine distribution of hyperfine magnetic fields and evolution of relative concentration of Fe-containing crystalline phases within the surface layer and the volume of the nanocrystallized ribbons with annealing temperature. Differential scanning calorimetry revealed two crystallization stages at T_x1 ～ 510 ^°C and T_x2 ～ 640 ^°C, connected to precipitation of α-Fe and Fe(Mo,B) nanocrystals, respectively. The amorphous and partially crystalline state was obtained by annealing at several temperatures in the range 510-650 ^°C. The combination of conversion electron (CEMS) and transmission Mössbauer spectrometry (TMS) showed that annealing induces crystallization starting from both surfaces of the ribbons. For the as-quenched sample, scanning electron microscopy (SEM) and CEMS revealed significant differences in the “air” and “wheel” sides of the ribbons, crystallites were preferentially formed at the latter. While SEM micrographs of annealed samples showed various mean diameters of the crystals at opposite sides of the ribbons, the amounts of crystalline volume derived from the CEMS spectra approximately equaled. Mössbauer spectra of annealed samples contained narrow sextet ascribed to crystalline α-Fe phase, three sextets with distribution of hyperfine field assigned to the interface regions of the nanocrystals and the contribution of the amorphous phases. In-field TMS performed at 4.2 K with magnetic moments aligned by external magnetic field enabled to properly determine in particular the contribution of the amorphous phases in the samples. Resulting distributions of the hyperfine fields were compared with ⁵⁷Fe(¹⁰B, ¹¹B) nuclear magnetic resonance (NMR) spectra.     

A Facile Synthesis of Novel Allenylphosphinates Containing Multi Potential Asymmetric Centers

The novel allenylphosphinates containing up to three axial and phosphorus asymmetric centers were prepared in excellent yields via the reactions of 6‐chloro‐6H‐dibenzo[c,e][1,2]oxaphosphinine to propargyl alcohols. During the process, the configuration of phosphorus determined the biphenyl axial chirality, stereospecifically forming (l)‐stereomers but did not influence the chirality of allenyl axis.     

Gröbner-Shirshov basis for degenerate Ringel-Hall algebras of type <Emphasis Type="Italic">F</Emphasis><Subscript>4</Subscript>

In this paper, by using the Frobenius morphism and the multiplication formulas of the generic extension monoid algebra, the authors first give a presentation of the degenerate Ringel-Hall algebra, and then construct the Gröbner-Shirshov basis for degenerate Ringel-Hall algebras of type F ₄.