New synthesis of β-lactams

α-Methylene-β-lactams 3 were synthesized from the various 2-bromoallylamine derivatives 2 using a catalytic amount of Pd(OAc)₂ or PD(acac)₂ and PPh₃, under 1–4 atom pressure of CO in good yields. Similarly, α-alkylidene-β-lactams 20 were synthesized from 3-alkyl-2-bromoallylamines 19, which were easily prepared from the olefins 14, in the same manner.     

2-乙酰噻吩及其新型席夫碱的合成

以磷钨酸为催化剂,噻吩和乙酸酐反应合成了2-乙酰噻吩(1,收率83.5%);1与不同结构的酰肼反应合成了四种新型席夫碱(2a～2d),收率90%～95%,其结构经UV,~1H NMR,~(13)C NMR,IR及元素分析表征.优化了合成1和2的反应条件.     

邻-二氨基烯的合成新方法

以芳香醛,硫和胺为起始原料,经Willgerodt—Kindler反应合成硫代酰胺,硫代酰胺在钐／二碘化钐试剂促进下发生脱硫偶联反应,得到邻-二氨基烯类化合物。其结构经1^H NMR,IR,MS和元素分析表征。     

新型氨基磺酸系高效减水剂的制备及性能研究

以纯碱替代氢氧化钠,同时采用双氧水作氧化剂,成功研制了一种新型氨基磺酸系高效减水剂(HP)。红外光谱和核磁共振分析表明,HP分子结构中含有-COO-、-SO3-、-OH、-NH2等多种官能团,而多种功能基团的合理组合并与链结构相匹配是制备高性能HP高效减水剂的关键所在。该减水剂与目前市售萘系减水剂相比,具有掺量低、减水率大及混凝土坍落度损失小、抗压强度高等优良性能,且制备工艺简单。     

合成双醋瑞因的新方法

以芦荟素为原料,经脱苷、氧化反应得到大黄酸(4);4经三氟甲磺酸锌催化的乙酰化反应合成了双醋瑞因,总收率86.2%,其结构经1H NMR,IR和MS确证。     

New Heterocyclic Analogues of Anthracycline Antibiotics

ABSTRACT

Synthetic approaches to anthracycline antibiotic analogues in which the nitrogen atom of the carbohydrate portion is incorporated into a 1, 2, 3-triazolyl moiety were investigated. By using methyl 6-azido-2, 6-dideoxy-β-D--arabino-hexopyranoside and methyl 6-azido-2, 3, 6-tricdeoxy--α-L-arabino-hexopyranoside, the corresponding glycosides (16 a, b - 18 a, b) of carminomycinone and daunomycinone were prepared. The desired heterocyclic system was developed directly with the C-3′ and C-6′ azido anthracyclines by means of a cycloaddition process to give 7-0-[6′-(4, 5--dicarboethoxy-l, 2, 3-triazolyl)-2′, 6′-dideoxy-β-D-arabino--hexopyranosyl]-carminomycinone (23) and -daunomycinone (22), and 3′-(4, 5-dicarboethoxy - l, 2, 3-triazolyl)-4′ -epi-daunomycin (24).     

New products

Summary An efficient and economical GC method for rapid determination of FAMEs in rapeseed-mustard is described. The seeds were transmethylated with acetylchloride, using microwave heating and separation achieved on a 3 m column packed with a mixture of 2% SP-2300 and 3% SP-2310 on Chromosorb ‘W’. The method is compared with the conventional heating method and extended efficiently for half-seed analysis. The fatty acid composition of the FAMEs mixtures prepared by both methods was similar with highly significant correlation coefficients (P<0.001).     

A New Prenylated Isoflavone and a New Flavonol Glycoside from Flemingia philippinensis

A new prenylated isoflavonoid, flemiphilippinin G ( 1 ), and a new flavonol glycoside, flemiphilippininside ( 2 ), along with eleven known isoflavonoids were obtained from the roots of Flemingia philippinensis (Merr. et Rolfe) Li . Their structures were elucidated on the basis of spectroscopic data. The in vitro cytotoxicities of compounds 1 – 13 against MCF‐7, A549, and Hep‐G2 cell lines were determined by using the MTT (=3‐(4,5‐dimethylthazol‐2‐yl)‐2,5‐diphenyl‐2H‐tetrazolium bromide) colorimetric assay, and their antioxidant activities were evaluated by ferric‐reducing antioxidant power (FRAP) method. Compound 1 exhibited significant cytotoxicity against all the tested cell lines with IC₅₀ values of 4.8–7.3 μM , and compound 2 was found to be inactive. Both compounds 1 and 2 showed weak antioxidant activities with FRAP values of 110±15 and 124±16 μmol/g, respectively.     

Conformational Properties of New Thiosemicarbazone and Thiocarbohydrazone Derivatives and Their Possible Targets

The structure assignment and conformational analysis of thiosemicarbazone KKI15 and thiocarbohydrazone KKI18 were performed through homonuclear and heteronuclear 2D Nuclear Magnetic Resonance (NMR) spectroscopy (2D-COSY, 2D-NOESY, 2D-HSQC, and 2D-HMBC) and quantum mechanics (QM) calculations using Functional Density Theory (DFT). After the structure identification of the compounds, various conformations of the two compounds were calculated using DFT. The two molecules showed the most energy-favorable values when their two double bonds adopted the E configuration. These configurations were compatible with the spatial correlations observed in the 2D-NOESY spectrum. In addition, due to the various isomers that occurred, the energy of the transition states from one isomer to another was calculated. Finally, molecular binding experiments were performed to detect potential targets for KKI15 and KKI18 derived from SwissAdme. In silico molecular binding experiments showed favorable binding energy values for all four enzymes studied. The strongest binding energy was observed in the enzyme butyrylcholinesterase. ADMET calculations using the preADMET and pKCSm software showed that the two molecules appear as possible drug leads.     

Synthesis of New Quinoxaline Derivatives

New quinoxaline derivatives were prepared by the reaction of 2-hydroxyquinoxaline 1 and alkyl or alkylaminoalkyl halides in dimethylformamide using potassium carbonate as a base. The hydroxyl group was readily converted into a thiol function by treatment with phosphorus pentasulfide and/or Lawesson's reagent in pyridine, and the subsequent alkylation of the thiol group was carried out under phase-transfer catalyst conditions. Chlorination of 1 was carried out with phosphorus oxychloride. Branching of alkylamino side chains to the 2-OH, 2-SH, and 2-Cl quinoxalines resulted in the synthesis of several compounds. Synthesis and alkylation of 2-hydroxy 7-nitroquinoxaline are also reported.      

Three New Diterpenoids from Euphorbia cheiradenia

Three new diterpene esters, cheiradone ( 1 ), cheiradone A ( 2 ), and cheiradone B ( 3 ), were isolated from the aerial parts of Euphorbia cheiradenia, collected in Iran. The structures were determined using different spectroscopic methods, including 1D and 2D NMR and X‐ray diffraction analysis.     

Synthesis and Microbial Studies of New Pyridine Derivatives-Ill

2-Amino substituted benzothiazole 4a--4I and p-acetamidobenzenesulfonyl chloride 2 were used to prepare 2-（p-aminophenylsulfonamido） substituted benzothiazole 6a--6I using mixture of pyridine and acetic anhydride which formed an electrophilic complex （N-acetyl pyridinium） to facilitate condensation to give desired product by removal of HC1. 2-{p-[（3-Carboxypyrid-2-y1）amino]phenylsulfonamido}benzothiazoles 8a--81 were synthesized from 2-chloropyridine-3-carboxylic acid 7 and 6a--6I in 2-ethoxy ethanol using Cu-powder and K2CO3. Acid chlorides 9a--91 were condensed with 2-hydroxyethyl piperazine 10 and 2,3-dichloropiperazine 11 for amide deriva- tives 2-（p-（（3-（4-（2-hydroxyethy1）piperazin-1-ylcarbonyl）pyrid-2-y1）amino）phenylsulfonamido）benzothiazoes 12a -121 and 2-{p-[3-（2,3-dichloropiperazin-l-ylcarbonyl）pyrid-2-ylamino]phenylsulfonamido}benzothiazoles 13a- 131 respectively. The structures of the new compounds have been established on the basis of their chemical analysis and spectral data （IR, 1↑H NMR and mass）. All the compounds have been screened for their antibacterial and antifungal activities.     

New luminescent polymers for leds and LECS

Statistical copolymers 5 containing poly(2-dimethyloctylsilyl-1,4-phenylenevinylene) (DMOS-PPV) and poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) have been synthesized using the dehydrohalogenation condensation route. The copolymers show a shift of photoluminescence maxima to longer wavelengths as the proportion of the MEH-PV unit increases. This trend is accompanied by reduced efficiencies and lower turn-on voltages in single layer electroluminescent devices. Light-emitting electrochemical cells (LECs) have been prepared using a blend of DMOS-PPV 1 with poly(ethylene oxide)/lithium triflate and the homopolymer poly[2-methoxy-5-(triethoxymethoxy)-1,4-phenylene vinylene] (MTEM-PPV) 9 with lithium triflate. In comparison with single-layer devices which were fabricated using the homopolymers 1 and poly[2,5-bis(triethoxymethoxy)-1,4-phenylene vinylene] (BTEM-PPV) 10 , the LEC devices showed lower turn-on voltages.     

New triterpene glycosides from Camptosorus sibiricus

Two new cycloartane glycosides were isolated from the whole herbs of Camptosorus sibiricus Rupr. By means of chemical and spectroscopic methods (1D and 2D NMR, HRMS, ESI-MS), the structures were established as (24R)-3beta,7beta,24,25,30-pentahydroxycycloartane-30-O-coumaroyl-3-O-beta-D-glucopyranosyl-24-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranoside (1) and (24R)-3beta,7beta,24,25,30-pentahydroxy-1-ene-cycloartane 24-O-beta-D-glucopyranoside (2). The two new compounds were inactive in vitro against A375-S2 and Hela human tumor cell lines using the MTT method.     

Synthesis of New 1,4-Dihydropyridine Derivatives Containing Thiazolyl Substituents

A series of 4-[2-methyl (or aryl) thiazole-4-yl]-2,6-dimethyl-3,5-diacetyl (or dibenzoyl) 1,4-dihydropyridines were synthesized using a modified Hantzsch reaction involving the condensation of the corresponding aldehyde with acetyl acetone or benzoyl acetone. The preparation of the corresponding aldehydes (2-methylthiazole-4-carboxaldehyde and some 2-arylthiazole-4-carboxaldehydes) was achieved by a simplified protocol of the published synthesis.     

New and efficient synthesis of bi- and trisubstituted indazoles

In this paper, the synthesis of bi- and trisubstituted indazoles was described. 4-Alkoxy-7-aminoprotected-indazole or 7-aminoprotected-indazole derivatives were prepared selectively using SnCl₂ in alcohol or SnCl₂ in ethyl acetate, respectively. The effects of the halogen atom in position 3 and of the N-alkylation in N-1 position of 7-nitroindazoles were investigated.     

A New Method for the Synthesis of Furan Derivatives

Substituted 2-chloro-4-formyl-5-arylfuran and 2,5-dimethyl-3-formylfuran derivatives were synthesised from their corresponding substituted 3-benzoylpropionic acid and acetonylacetone using Vilsmeier reagent in good yields.     

抗高血压新药DDPH的晶体结构

1－（2，6-二甲基苯氧基）－2－（3，4二甲氧苯乙胺基）丙烷盐酸盐（简称DDPH）是一种降血压新药。用X射线衍射法测定了两个晶体结构，（±）DDPH和（＋）DDPH单晶的空间群分别为P21/a和P212121。（±）DDPH分子呈弓形，整体近似一个平面结构；（＋）DDPH的2个苯环夹角较大，整个分子比较伸展。     

2,3-二甲基-5,6-二烷基吡嗪新香料的合成

2 ,3 二甲基 5 ,6 二烷基吡嗪是一类重要的有机合成中间体和香料 ,在过去几十年已从咖啡、花生、爆米花、炒核桃、炸土豆等食品中广泛检测出它们的存在 ,是构成这类食物香味的微量有效成分之一[1 ] 。这类香料因其香味强、用量少、安全可靠而受到重视 ,现已有十余种烷基吡嗪类香料实现了商业化生产。合成烷基吡嗪的传统方法是用邻二胺和邻二酮缩合氧化制得[2 ] ,但由于受原料来源的限制 ,不利于新型香料品种的开发。缺电子环状共轭体系的自由基烷基化反应是在这类体系中引入烷基的有效方法之一 ,Ｔｏｒｓｓｅｌｌ等[3] 先后用自由基烷基化反…     

Synthesis and Conductivity of a New Series of Organometallic Charge Transfer Salts

In order to study the relationship between structure and conductivity, ten new organometallic radical ionic salts. [CpFeBz]_n[M(mnt)₂] and [CpFeBz]_n[M(dmit)₂] (M=Ni, Pd, Pt, Cu, Co; Cp=Cydopentadienyl; Bz=Benzene; H₂mnt=maleonitriledithiole; H₂dmit=4,5-dimercapto-1, 3-dithioie-2-thione; n=1 or 2), were synthesized according to a new synthetic route. They were characterized using elemental analysis, infrared and ¹H-nuclenr magnetic reso-nance spectroscopy. The crystal structure of [CpFeBz]₂[Ni(mnt)₂] was determined using X-ray diffraction. The electrical conductivity of siolid stale was reported. Gomplexes of [CpFeBz]_n[M(mnt)₂] showed a low conductivity, while complexes of [CpKeBz]_n[M(dmit)₂] exhibited a rather high conductivity in the range of 10^-1-10^-2S·cm^-1.