CIDNP study of the photochemistry of 1-acetylindole-2,3-dione

Chemically Induced Dynamic Nuclear Polarization (CIDNP) technique is applied to study the photochemical reactions of 1-acetylindole-2,3-dione (AID) with several hydrogen do- nors (1—13). These reactions take place by direct hydrogen abstraction of triplet excited AID from the corresponding 1—13 to give neutral radical pair intermediates, which afford polarized starting materials by back hydrogen transfer and give polarized coupling products by radical pair recombination.

Palladium-catalyzed stereoselective decarboxylative[4+2]cyclization of 2-methylidenetrimethylene carbonates with pyrrolidone-derived enones:Straightforward access to chiral tetrahydropyran-fused spiro-pyrrolidine-2,3-diones

A novel asymmetric[4+2]cycloaddition of 2-methylidenetrimethylene carbonate with pyrrolidonederived enones has been achieved to produce the functionalized tetrahydropyran-fused spirocyclic scaffolds via palladium-catalysis.An array of enantioenriched spiro-pyrrolidine-2,3-diones bearing adjacent quaternary and tertiary stereocenters are obtained in high yields with excellent enantioselectivities(up to 96% yield and 99% ee).The further transformation of the product has been accomplished for the construction of medical interesting β^(2,2)-amino acids and β-lactams.Preliminary mechanistic research was well conducted.

Transformations of N-arylpropiolamides to indoline-2,3-diones and acids via C≡C triple bond oxidative cleavage and C(sp^2)–H functionalization

A new palladium-catalyzed oxidative conversion of N-arylpropiolamides and H2O to various indoline-2,3-diones and acids through the C≡C triple bond cleavage and C(sp2)–H functionalization is described,which is promoted by a cooperative action of catalytic CuBr2,2,2,6,6-tetramethyl-1-piperidinyloxy(TEMPO)and O2.The method provides a practical tool for transformations of alkynes by means of a C–H functionalization strategy,which enables the formation of one C–C bond and multiple C–O bonds in a single reaction with high substrates compatibility and excellent functional group tolerance.

A facile one-pot synthesis of new thieno-[2,3-d]pyrimidine-2,4(1H,3H)-dione derivatives

A facile one-pot synthesis of new 3-arylthieno[2,3-d]pyrimidine-2,4（1H,3H）-diones via base-catalyzed cyclocondensation of ethyl 2-amino-4,5-dimethylthiophene-3-carboxylate with aryl isocyanates is described.

Determination of Trace Silver( Ⅰ ) in Basic Aqueous Solution by Electrochemiluminescence of a New Reagent 6-(2-Hydroxy-4-Diethylaminophenylazo)-2,3-Dihydro-1,4-Phthalazine-1,4-Dione

The electrochemiluminescence (ECL) of a new reagent 6- (2-hydroxy- 4 diethy laminophenylazo)-2,3-dihydro-1 ,4-phthalazine-1,4-dione (HDEA) in a basic aqueous so lution was studied by using the apparatus designed by ourselves. Trace amounts of silver ( Ⅰ ) shows a significant effect on the efficiency of light emission of HDEA during a positive trigonometrical wave pulse was exerted on the solution. The linear relationship between the light intensity and the concentration of silver( Ⅰ ) occurs in the range of 5. 0×10-8 to 3. 0×10-8 mol/L Ag(Ⅰ ) in a medium of KOH-KCl-HDEA (pH= 12. 8). The detection limit of the method is 2. 0×10-8 mol/LAg( Ⅰ ), and the r. s. d. for 1.0×10-7 mo)/L Ag ( Ⅰ ) is 5%. Of 21 metal ions concerned, only nickel( Ⅱ ), cerium( Ⅳ ) and cobalt( Ⅱ ) interfere the silver detection seriously; Ⅰ and Br also have some interference.

Synthesis and Biological Evaluation ofPyrano[2,3-f]chromene-4,8-dione Derivatives as Potential Anticancer Agents

Based on the hit 5-hydroxy-2-methyl-10-propyl-2,3-dihydro-4H,8H-pyrano[2,3-j]chromene-4,8-dione（1）, a series of pyrano[2,3-f]chromene-4,8-dione derivatives was designed and synthesized using pb_loroghicinol as startingmaterial. Meanwhile, a regioselective synthetic route was developed for 5-methoxy-2,3-dihydro-4H,8H-pyrano-[2,3-f]chromene-4,8-dione products（11a-11f）, and their structures were further confirmed by nuclear Overhausereffect（NOE）. The evaluation of anticancer activities of these compounds against four human cancer cell lines,including human glioma cell line （SHG-44）, human lung cancer cell line（H1299）, breast cancer cell line（/vICF7） andhuman colon carcinoma cell line（HCT-116） in vitro shows that 5-methoxy-2,2-dimethyl-9-chloro-10-trifluormethyl-2,3-dihydro-4H,8H-pyrano[2,3-f]chromene-4,8-dione（lle） possesses the best anticancer activities with IC50 values of6.68, 7.90, 5.16 and 4.82 gmol/L, respectively. Finally, the preliminary structure-activity relationships（SARs） weresttmmarized, which could pave the way for generating more potent anticancer agents with drug-like properties.

Optimizing polymer aggregation and blend morphology for boosting the photovoltaic performance of polymer solar cells via a random terpolymerization strategy

Compared to regular conjugated polymers,the random conjugated terpolymers are usually not beneficial to achieve highly efficient non-fullerene(NF)-based polymer solar cells(PSCs)due to their disordered chemical structures.In this work,we report two random terpolymer donors(PBNB80 and PBNB50)by tuning the molar ratio of electron-accepting units of 1,3-di(thiophen-2-yl)naphtho[2,3-c]thiophene-4,9-dione(NTD)and 1,3-bis(4-chlorothiophen-2-yl)-4 H,8 H-benzo[1,2-c:4,5-c’]dithiophene-4,8-dione(ClBDD),at the same time,the parent polymers(PBNB100 and PBNB00)are also compared to study.These four polymer donors exhibit similar optical bandgaps and gradually deepen highest occupied molecular orbital levels.Importantly,aggregation and self-organization properties of the random terpolymer donors are optimized,which result in the better morphology and crystal coherence length after blending with NF acceptor of BO-4 Cl.Particularly,a PBNB80:BO-4 Cl blend forms an optimal nanoscale phase-separation morphology,thereby producing an outstanding power conversion efficiency of 16.0%,which is much higher than those(12.8%and 10.7%)of their parent binary polymer donor-based devices.This work demonstrates that rational using terpolymerization strategy to prepare random terpolymer is a very important method to achieve highly efficient NF-PSCs.

红葱的化学成分研究

目的研究红葱Eleutherine americana的化学成分。方法采用硅胶柱色谱、Sephadex LH-20柱色谱及重结晶等方法,分离纯化红葱的化学成分,通过MS、NMR等波谱技术确定化合物结构。结果确定了7个化合物的结构,分别为9-hydroxy-8-methoxy-1-methyl-1,3-dihydronaphtho[2,3-c]furan-4-O-β-D-glucopyranoside(1)、eleutherinoside A(2)、豆甾醇-3-O-β-D-葡萄糖苷(3)、kadsuric acid(4)、豆甾醇(5)、1,2-二羟基-8-甲氧基-3-甲基蒽醌(6)、9-methoxy-1,3-dimethyl-1H-naphtho[2,3-c]pyran-5,10-dione(7)。结论化合物1为新化合物,命名为红葱新苷。化合物3～5为首次从该植物中分离得到,化合物6和7为首次获得的新天然产物。

Brφnsted acidic ionic liquid catalyzed highly efficient synthesis of chromeno pyrimidinone derivatives and their antimicrobial activity

A series of 8,9-dihydro-2-（2-oxo-2H-chromen-3-yl）-5-aryl-3H-chromeno[2,3-d]pyrimidine-4,6（5H^7H）-diones （Sa-j）have been synthesized by the reaction of 2-amino-5,6,7,8-tetrahydro-5-oxo-4-aryl-4H-chromene-3-carbonitrile （4a-j） with couma- rin-3-catboxylic acid under neat conditions employing Brnsted acidic ionic liquid （4-sulfobutyl）tris（4-sulfophenyl）phosphonium hydrogen sulfate as catalyst. Structures of all the compounds were established on the basis of analytical and spectroscopic data. All the compounds were evaluated for their in vitro antimicrobial activity against different bacterial and fungal strains.