Effects of the structure of the branches on the two-photon absorption properties for the multi-branched molecules with nitrogen (N) as coupling center

In order to investigate the effects of the structure of branches on the TPA properties for multi-branched molecules, the TPA cross section is calculated by using ZINDO/SOS method. The investigated mole- cules have different branches (chomorfores based on stilbene, dithienothiophene and flourene) with nitrogen(N) as coupling center. The results show that the cooperative enhancement in multi-branched molecules depends on the structures of the branches and the structures of branches play an important role in the enhancement of the TPA cross section. The designed molecules with stilbene and dithie- nothiophene as branched possess relatively larger two-photon absorption cross sections.     

Cu（I）-Catalyzed Synthesis of 2-Substituted Benzimidazoles from 2-lodoanilines and Amides

A novel and efficient approach to the synthesis of 2-substituted benzimidazoles has been developed via CuI/DMEDA-catalyzed coupling reaction and post-cyclization with glacial acetic acid from readily available 2-iodoanilines and amides. This method is suitable for the construction of a variety of benzimidazoles in moderate to good yields under short reaction times.     

CuI/Proline-catalyzed N-Arylation of Nitrogen Heterocycles

Qing Xiang GUON-Arylated heterocycles such as pyrroles, indoles, and imidazoles are important building blocks for the synthesis of natural products, pharmaceuticals, and function materials1. Usually these compounds were synthesized by Cu-catalyzed Ullmann…     

Bismuth Mediated Organic Reaction: A Convenient Method for the Synthesis of Allylic (Benzylic) Selenides and α-Organylselenocarbonyl Compounds in Aqueous Media

Organic reactions promoted by active metals have aroused much interest in recent years. Active bismuth has been used in Barbier-type reaction of allylic halides with aldehydes1 and aldimines2 as well as Reformatzky type reaction3. Other publications referred to the cross coupling between aldehydes and α-diketones4, the substitution to benzotriazole drivatives5 and the reductive coupling reaction of nitro compounds6. These reactions generally promoted by elemental bismuth generated in situ fr…     

5-Hexylidene-4-propylamino-1,5-dihydroimidazol-2-one formed from Cu-catalyzed oxidation with implication for the structure of a His-Lys cross-link

Cu-catalyzed oxidation of 5-hexyl-1,3-dihydroimidazo-2-one(1)in the presence of propylamine,as surrogates for the oxidized His side chain and Lys side chain,was investigated.5-Hexylidene-4-propylamino-1,5-dihydroimidazol-2-one(2),a model His-Lys cross-link product,was isolated and structurally characterized by NMR and mass spectrometry.     

Synthesis of Enamines via the Cross-coupling of Thioamides and Diarylketones Promoted by the Sm/SmI2 Mixed Reagent

Since 1977 samarium diiodide has been widely used to promote a lot of reductive and coupling reactions1. Utilizing the samarium/samarium diiodide mixed reagent, Ogawa performed the intermolecular reductive deoxygenative coupling of amides2. Our group has …     

ELECTRODIALYTIC PRODUCTION OF HYPOPHOSPHOROUS ACID

1. INTRODUCTIONHypophosphorous acid (H3PO2) also known as phosphinic acid, is currently a staple article of commerce which is sold by various companies for purposes such as the manufacture of hypophosphite salts, as well as to prevent the discoloration of phosphate esters, in esterification catalysts, and for the manufacture of cooling water treatment chemicals. It is also sold for use in metal finishing procedures, as a reducing agent for electroless plating, and as a sealer for phosphat…     

Synthesis of Diethyl Oxalate by a Coupling-Regeneration Reaction of Carbon Monoxide

This article describes a process for the synthesis of diethyl oxalate by a coupling reaction of carbon monoxide, catalyzed by palladium in the presence of ethyl nitrite. The kinetics and mechanism of the coupling and regeneration reaction are also discussed. This paper presents the results of a scale-up test of the catalyst and the process based on an a priori computer simulation.     

Porous polymer supported palladium catalyst for cross coupling reactions with high activity and recyclability

Porous polymer supported palladium catalyst for cross coupling reactions with high activity has been successfully prepared by coordination of Pd 2+ species with Schiff bases functionalized porous polymer. The catalyst has been systemically investi-gated by a series of characterizations such as TEM, N 2 adsorption, NMR, IR, XPS, etc. TEM and N 2 isotherms show that the sample maintains the nanoporous structure after the modification and coordination. XPS results show that chemical state of palladium species in the catalyst is mainly +2. More importantly, the catalyst shows very high activities and excellent recycla-bility in a series of coupling reactions including Suzuki, Sonogashira, and Heck reactions. Hot filtration and poison of catalysts experiments have also been performed and the results indicate that soluble active species (mainly Pd(0) species) in-situ gener-ated from the catalyst under the reaction conditions are the active intermediates, which would redeposit to the supporter after the reactions.     

Catalytic diastereoselective and enantioconvergent C(sp~3)–C(sp~3) cross-coupling of racemic partners

正Carbon-carbon bond formation is the core of organic synthesis.Transition metal-catalyzed cross-coupling reaction between organohalides and organometallic reagents is one of the most important and straightforward methods for construction of C-C bonds.The catalytic cross coupling between two sp~2-carbon centers,e.g.,aryl-aryl cross-     

钨酸钠催化芳香腈高选择性氧化制备芳香酰胺

 The preparation of aryl amides by selective oxidation of aryl nitriles using sodium tungstate as catalyst and sodium percarbonate or sodium carbonate-hydrogen peroxide as the oxidant in a methanol and water solution was studied. Aryl nitriles were converted to aryl amides with very high selectivity of 95%～100% at room temperature. The reactivity of aryl nitriles decreased with increasing their branched chain length. In the oxidation of tolunitriles, the oxidation rate of p-tolunitrile and m-tolunitrile was very fast, but the oxidation rate of o-tolunitrile was very slow. The oxidation rate of p-haloid aryl nitriles and p-nitro aryl nitrile decreased in the order p-nitrobenzonitrile＞p-chlorobenzonitrile＞p-bromobenzonitrile, while the selectivity for aryl amides was maintained at a high level of 98%～100%. The comparison of the two oxidants showed that when sodium carbonate-hydrogen peroxide was used as oxidant, the oxidation rate and selectivity were better than that when percarbonate was used. The sodium tungstate catalyst and carbonate can be reused and the catalytic activity and selectivity did not change if a suitable amount of hydrogen peroxide was supplied. This work provides a convenient method for the preparation of aryl amides from aryl nitriles under very mild reaction conditions.     

时域反射光谱法研究酰胺-醇混合物的介电驰豫

Using time domain reflectometry （TDR）, dielectric relaxation studies were carded out on binary mixtures of amides （N-methylformamide （NMF） and N,N-dimethylformamide （DMF）） with alcohols （1-butanol, 1-pentanol, 1- hexanol, 1-heptanol, 1-octanol, and 1-decanol） for various concentrations over the frequency range from 10 MHz to 10 GHz at 303 K. The Kirkwood correlation factor and excess dielectric constant properties were determined and discussed to yield information on the molecular interactions of the systems. The relaxation time varied with the chain length of alcohols and substituted amides were noticed. The Bruggeman plot shows a deviation from linearity. This deviation was attributed to some sort of molecular interaction which may take place between the alcohols and substituted amides. The excess static permittivity and excess inverse relaxation time values varied from negative to positive for all the systems indicating that the solute-solvent interaction existed between alcohols and substituted amides for all the dynamics of the mixture.     

First Magnesium-mediated Carbonyl Benzylation in Water

Catalyzed by AgNO3, Mg was found for the first time to be able to mediate the coupling reaction between aromatic aldehydes and benzyl bromide or chloride in water. The yields were slightly higher than the recent results for Mg-mediated allylation despite the fact that aqueous benzylation is intrinsically much harder than allylation. It was also found that the coupling reaction was chemoselective for aromatic aldehydes over aliphatic aldehydes, and chemoselective for aromatic aldehydes over aromatic ketones.     

时域反射光谱法研究酰胺-醇混合物的介电驰豫

Using time domain reflectometry (TDR),dielectric relaxation studies were carried out on binary mixtures of amides (N-methylformamide (NMF) and N,N-dimethylformamide (DMF)) with alcohols (1-butanol,1-pentanol,1-hexanol,1-heptanol,1-octanol,and 1-decanol) for various concentrations over the frequency range from 10 MHz to 10 GHz at 303 K. The Kirkwood correlation factor and excess dielectric constant properties were determined and discussed to yield information on the molecular interactions of the systems. The relaxation time varied with the chain length of alcohols and substituted amides were noticed. The Bruggeman plot shows a deviation from linearity. This deviation was attributed to some sort of molecular interaction which may take place between the alcohols and substituted amides. The excess static permittivity and excess inverse relaxation time values varied from negative to positive for all the systems indicating that the solute-solvent interaction existed between alcohols and substituted amides for all the dynamics of the mixture.     

Direct synthesis of imines by 9-azabicyclo-[3,3,1]nonan-N-oxyl/KOH-catalyzed aerobic oxidative coupling of alcohols and amines

A simple and efficient method for preparation of imines by the oxidative coupling of alcohols and amines using ABNO/KOH as the catalysts, and air as the economic and green oxidant was developed.     

Mechanistic study of copper-catalyzed intramolecular ortho-C-H activation/carbon-nitrogen and carbon-oxygen cyclizations

Intramolecular ortho-C-H activation and C-N/C-O cyclizations of phenyl amidines and amides have recently been achieved under Cu catalysis. These reactions provide important examples of Cu-catalyzed functionalization of inert C-H bonds, but their mechanisms remain poorly understood. In the present study the several possible mechanisms including electrophilic aromatic substitution, concerted metalation-deprotonation (CMD), Friedel-Crafts mechanism, radical mechanism, and protoncoupled electron transfer have been theoretically examined. Cu(Ⅱ)-assisted CMD mechanism is found to be the most feasible for both C-O and C-N cyclizations. This mechanism includes three steps, i.e. CMD with Cu(Ⅱ), oxidation of the Cu(Ⅱ) intermediate, and reductive elimination from Cu(Ⅲ). Our calculations show that Cu(Ⅱ) mediates the C-H activation through an six-membered ring CMD transition state similar to that proposed for many Pd-catalyzed C-H activation reactions. It is also interesting to find that the rate-limiting steps are different for C-N and C-O cyclizations: for the former it is concerted metalation-deprotonation with Cu(Ⅱ), whereas for the latter it is reductive elimination from Cu(Ⅲ). The above conclusions are consistent with the experimental kinetic isotope effects (1.0 and 2.1 for C-O and C-N cyclizations, respectively), substituent effects, and the reactions under O2 -free conditions.     

Organophosphorus Compound DEPBT as a Coupling Reagent for Oligopeptides and Peptoids Synthesis：Studies on Its Mechanism

Some oligopeptides and peptoids were synthesized by applying the organophosphorus compound DEPBT as a coupling reagent. D-Biotin-OOBt was obtained unexpectedly. A proposed reaction mechanism for DEPBT-mediated coupling was proved.     

Recognition for avian influenza virus proteins based on support vector machine and linear discriminant analysis

Total 200 properties related to structural characteristics were employed to represent structures of 400 HA coded proteins of influenza virus as training samples. Some recognition models for HA proteins of avian influenza virus (AIV) were developed using support vector machine (SVM) and linear discriminant analysis (LDA). The results obtained from LDA are as follows: the identification accuracy (Ria) for training samples is 99.8% and Ria by leave one out cross validation is 99.5%. Both Ria of 99.8% for training samples and Ria of 99.3% by leave one out cross validation are obtained using SVM model, respectively. External 200 HA proteins of influenza virus were used to validate the external predictive power of the resulting model. The external Ria for them is 95.5% by LDA and 96.5% by SVM, respectively, which shows that HA proteins of AIVs are preferably recognized by SVM and LDA, and the performances by SVM are superior to those by LDA.     

Synthesis of nucleoside tetraphosphates and dinucleoside pentaphosphates from nucleoside phosphoropiperidates via the activation of P(V)-N bond

A novel and efficient method for the preparation of nucleoside 5’-tetraphosphates has been developed by coupling nucleoside 5’-phosphoropiperidates with triphosphate reagent in the presence of 4,5-dicyanoimidazole(DCI) activator.Further coupling of the nucleoside 5’-tetraphosphates with nucleoside 5’-phosphoropiperidates via the P(V)-N activation strategy provided a reliable synthetic method for both symmetrical and asymmetrical dinucleoside pentaphosphates.