N-(4''''-取代嘧啶-2''''-基)-2-甲氧羰基-5-(取代)苯甲酰胺基苯磺酰脲化合物的合成及除草活性研究

为进一步寻找高效、安全和对环境更加友好的除草剂,以商品化除草剂单嘧磺酯为研究基础,对其结构中的苯环5-位取代基作了结构修饰,合成了26个未见文献报道的新型N-(4'-取代嘧啶-2-基)-2-甲氧羰基-5-苯甲酰胺基苯磺酰脲化合物,通过1H NMR、质谱及元素分析确定了化合物的结构.经油菜平皿法及盆栽法测试了所有化合物的除草活性,结果表明,当苯环5-位取代基为苯甲酰胺时,活性较好,其对双子叶植物的除草活性与商品化的甲嘧磺隆相当.     

新型吖啶-9-磺酰胺衍生物的合成及光谱学性质

在吖啶磺酰胺分子中引入杂环安替比林吸电性基团,合成了N-对甲基苯磺酰基-N-(4-安替比林)-10-甲基吖啶-9-磺酰胺三氟甲基磺酸鎓盐.最终产物与未甲基化的前体分别与模型化合物N-对甲基苯磺酰基-N-苯基-10-甲基吖啶-9-酰胺三氟甲基磺酸鎓盐及其前体的紫外-可见吸收光谱(UV)、荧光光谱(FL)进行比较.结果表明,引入杂环安替比林使吖啶磺酰胺的UV和FL谱发生了变化,尤其是FL谱的最大激发与发射峰的位置比相应的模型化合物大幅蓝移.最终产物及其前体的最大λex分别为268和274 nm; λem分别为321和327 nm.而模型化合物及前体最大λex分别为365和359 nm; λem分别为504和440 nm.H2O2引发的目标产物的化学发光(CL)在1.1 s完成;化学发光量子产率与模型化合物相当,是Luminol的化学发光效率的5.6倍.     

N-(4'-取代嘧啶-2'-基)-2-甲氧羰基-5-(取代)苯甲酰胺基苯磺酰脲化合物的合成及除草活性研究

为进一步寻找高效、安全和对环境更加友好的除草剂, 以商品化除草剂单嘧磺酯为研究基础, 对其结构中的苯环5-位取代基作了结构修饰, 合成了26个未见文献报道的新型N-(4'-取代嘧啶-2'-基)-2-甲氧羰基-5-苯甲酰胺基苯磺酰脲化合物, 通过¹H NMR、质谱及元素分析确定了化合物的结构. 经油菜平皿法及盆栽法测试了所有化合物的除草活性, 结果表明, 当苯环5-位取代基为苯甲酰胺时, 活性较好, 其对双子叶植物的除草活性与商品化的甲嘧磺隆相当.     

α-芳基-α-羟基酮(酯)与全氟烷基磺酰氟/甲基三乙氧基硅烷/碱体系不期望的氧化反应

研究了全氟烷基磺酰氟/甲基三乙氧基硅烷/碱体系与α-芳基-α-羟基酮(酯)化合物不期望的氧化反应, 以中等到优良的收率生成了相应的1,2-二酮(α-酮酸酯)产物. 所用全氟烷基磺酰氟为全氟正丁基磺酰氟或全氟正辛基磺酰氟; 碱为1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU). 提出了一种可能的反应机理. 为制备芳基取代的1,2-二酮(或α-酮酸酯)化合物提供了一种新方法.     

新型O-取代苯磺酰羟胺化合物的合成及其热性能

以O-取代苯磺酰氯和乙酰羟肟酸乙酯为原料，经消除、水解反应合成了6个新型的O-取代苯磺酰羟胺化合物：O-2-硝基苯磺酰羟胺、O-3-硝基苯磺酰羟胺、O-2,4-二硝基苯磺酰羟胺、O-2,4-二甲基苯磺酰羟胺、O-2,4,6-三甲基苯磺酰羟胺和O-2,4,6-三异丙基苯磺酰羟胺，其结构经¹H NMR, ¹³C NMR, IR和元素分析表征。并初步探讨了可能的反应机理。利用差示扫描量热分析(DSC)研究了化合物的热性能。结果表明：苯环上取代基供电子能力越强，化合物的热稳定性越好。     

苯环5位取代磺酰脲类化合物的水解动力学及三维定量构效关系初步研究

研究了除草活性较好的9个新型苯环5位取代的磺酰脲类化合物(A~I)分别在酸性、中性及碱性水溶液中的水解情况.采用HPLC-MS对水解产物进行分离鉴定,推测了水解产物的结构及水解路径.采用比较分子力场(Co MFA)方法,对化合物的结构与水解半衰期之间的关系进行了三维定量构效关系(3D-QSAR)研究.结果表明,苯环5位取代的苯磺酰脲类化合物的水解遵循一级动力学反应,容易发生酸性条件下的水解,水解反应第一步主要为酸催化下磺酰脲桥的断裂,形成5位取代的苯磺酰胺和氨基杂环.苯环5位取代的苯磺酰胺进一步发生5位酰胺基的水解,最后得到化合物c(6-氨基糖精)和d(糖精).苯环5位经修饰改造后,在相同条件下,其水解速度明显高于改造前的母体化合物单嘧磺酯和甲磺隆.苯环5位为酰胺基取代的化合物的水解速度随酰胺基上烷基碳原子数的增加及烷基体积的增大而降低.经计算所得的Co MFA模型能够对该系列化合物的水解半衰期进行较好的预测.     

cis-2,12-二取代环十二酮的合成及晶体结构

以环十二酮为原料合成了cis-2-苯磺酰基-12-苄基环十二酮、2-苯磺酰基-12-溴代环十二酮和2,12-二苄基环十二酮,它们的结构通过1H NMR,13C NMR和元素分析表征.化合物4的晶体结构参数:C25H32O3S,Mr=412.57,三斜晶系,空间群P1,a=0.96531(4)nm,b=1.12703(5)nm,c=1.17486(5)nm,α=89.278(2)°,β=75.582(2)°,γ=65.385(2)°,V=1.11938(8)nm3,Dc=1.224 g/cm3,Z=2,F(000)=444,μ(Mo Kα)=0.167 mm-1,S=1.038.化合物6的晶体结构参数:C18H25BrO3S,Mr=401.35,三斜晶系,空间群P1,a=0.77771(16)nm,b=1.0143(2)nm,c=1.2040(2)nm,α=89.46(3)°,β=80.13(3)°,γ=75.27(3)°,V=0.9044(3)nm3,Dc=1.474 g/cm3,Z=2,F(000)=416和μ(Mo Kα)=2.400 mm-1,S=1.042.cis-2-苯磺酰基-12-苄基环十二酮和cis-2-苯磺酰基-12-溴代环十二酮的X射线衍射结果表明,环十二酮母体骨架采取[3333]-2-酮构象,较小的取代基位于角顺位,较大的取代基位于边外向位.     

2-芳氧基-5-苯基-1,3,4-噁二唑类化合物的合成

本文通过芳氧基负离子在2—甲磺酰基—苯基—1,3,4—噁二唑环2—位上的亲核取代反应制得9个新的2—芳氧基—5—苯基—l,3,4—噁二唑衍生物。所有化合物的结构经元素分析,IR,~1H NMR和MS确认。初步抗菌实验表明这些化合物具有一定的抑制枯草芽孢杆菌繁殖的活性。 2,5—二取代l,3,4—噁二唑衍生物具有广泛的生物活性,如抗菌,抗黄球菌,除草杀棉花牙虫等。Madhavan等曾通过芳胺在2— 甲磺酰基—5—芳基1,3,4—噁二唑环上的亲核取代反应,制得了2—芳氨基—5—芳基—l,3,4—噁二唑衍生物,我们也曾通过酰肼等亲核试剂在2—甲磺酰基—5—(3,4,5—三甲氧基苯基)—1,3,4—噁二唑环上的亲核取代反应,得到了2—取代酰肼基—5—(3,4,5—三甲氧基苯基)—l,3,4—噁二唑衍生物。在此基础上,我们拟通过Aro在2—甲磺酰基     

3-羰基-4-氮杂-△5-雄甾烯-17-肟衍生物的合成及其抑制5α-还原酶活性研究

以雄甾-4-烯-3,17-二酮(AD)为起始原料,合成了14个甾体17位肟醚和肟酯类新化合物.所合成的化合物结构均经过MS,1H NMR谱确证,并对所合成的化合物进行了老鼠5α-还原酶抑制生物活性初步评价.结果表明：受试化合物均有一定的5α-还原酶抑制活性,其中化合物5a,5c,5d有较高的5α-还原酶抑制活性,与参比药物Espristeride相当.     

磺酰氯与不饱和化合物的反应

磺酰氯是一类重要的有机合成中间体,广泛应用于有机和药物合成中。磺酰氯可以作为烯砜、磺酰基、次磺酰基、芳基、氟代烷基等的来源应用于多种有机合成反应中。本文综述了磺酰氯与烯烃、炔烃、(杂)芳香环、亚胺、卤代醛酮等不饱和化合物的反应,主要包括[2+2]环合反应、氯磺酰化、磺酰化、次磺酰化、芳基化和氟代烷基化等反应,并讨论和预测了磺酰氯与不饱和化合物反应今后的发展方向。     

气相渗透法测定数均分子量的仪器常数问题研究

讨论了蒸气压渗透计仪器常数的分子量依赖性问题．通过对某些已知分子量化合物的温差信号随时间变化的研究，提出了测量四个低分子一种改进的ＶＰＯ信号的测量手续和数据处理方式，可以得到更为准确的数均分子量．     

PHOTOBIOLOGICAL ACTIVITY IN YEAST OF DERIVATIVES OF PSORALEN SUBSTITUTED AT THE 3,4 AND/OR THE 4',5' REACTION SITE

Abstract— Derivatives of psoralen substituted at the position 3 and/or 5' with various substituents (CN, CO-R or COO-R) have been newly synthesized. Their photobiological reactivity was determined by measuring the effects on survival and the induction of cytoplasmic 'petite' mutations (rho-) in the haploid yeast Saccharomyces cereuisiae after treatment with 365-nm irradiation in the presence of the different compounds. The effects were compared to those of known mono-functional compounds such as angelicin, 3-carbethoxypsoralen and 5,7-dimethoxycoumarin and bi-functional compounds such as psoralen and 8-methoxypsoralen for which the photoaffinity to DNA is well known. The derivative carrying a CN group in position 3 of the psoralen molecule exhibited effects comparable to those of the bi-functional agent 8-methoxypsoralen. Three derivatives substituted at position 3 showed a biological activity comparable to those of the mono-functional agent 3-carbethoxypsoralen. Two compounds substituted at position 5' by COOH or COOCH₃-groups were much less photobiologically active than the corresponding derivatives substituted in position 3. This suggested that the furanic site of the psoralen molecule may be photobiologically more active than the 3,4 site. Four newly synthesized angular derivatives, i.e. furo (2,3 f, g) coumarins, were found to be two to three times less active than angelicin.
At the dose rate of 365-nm irradiation used the measure of survival and rho^- induction per viable cell allowed the classification of some of the compounds as mono- and some as bi-functional agents in analogy to known mono- and bi-functional compounds.     

酚醛泡沫闭孔率测试方法及其主要影响因素的研究

用真密度仪研究了酚醛泡沫闭孔率的测试方法,在测试过程中对不同测试压力下体系达到平衡的时间进行跟踪,并结合扫描电镜观察泡沫在不同压力下测试前后的结构变化,进而对测试压力加以优化选择;利用扫描电镜观察了不同闭孔率酚醛泡沫的微观结构,深入讨论了酚醛泡沫闭孔率与不同微观结构的关系;对不同放置时间的样品进行恒温处理,将处理前后样品的闭孔率、微观结构进行对比分析.结果表明,优化测试条件、确定测试压力是保证闭孔率测试结果高效准确的首要前提;泡沫微观结构缺陷(如针孔、裂纹),是造成泡沫闭孔率低的直接原因;泡沫微观孔结构规整度、后处理程度的差异,是影响闭孔率测试过程(如测试时间过长,体系不易达到平衡)的主要因素.     

气相渗透法中的溶质吸附效应

在气相渗透仪上，用四个低分子量有机化合物和五个已知平均分子量的窄分布聚苯乙烯低聚体，对ＶＰＯ方法中的溶质吸附效应作了研究，提出了一种对吸附效应作改正的方法．所得结果表明，在扣除溶质吸附效应后，仪器常数Ｋ无分子量依赖性，提高了测定低分子量聚合物数均分子量的准确性．     

一种用于研究金属氢化反应的量热系统

将RD-1型量热计的样品管改装成能测量金属氢化反应热效应的量热系统,量热计常数经电能标定,峰高法和面积法所测结果的相对精度为0.5-1％。     

A SPECIFIC AND SENSITIVE METHOD FOR THE DETERMINATION OF BENZILIC ACID

Abstract

A specific, sensitive and relatively simple procedure is described for the quantitative analysis of benzilic acid. The method is based on α-naphthofuchsone formation obtained by condensation of benzilic acid with α-naphthol in the presence of concentrated sulfuric acid and measuring the resultant hydroxytriaryl methyl cation at 558 mμ. No interference was observed with other glycolic acid derivatives or oxygen-bearing compounds. As little as 5 × 10^?6 M benzilic acid is determinable.     

Synthesis and surface-active properties of fluorinated cyclic PEGyl succinate derivatives

Equimolar reaction of PEG with maleic anhydride in favoring conditions to cyclization is described. The obtained cyclic compounds were submitted to radical addition of 2-F-alkylethanethiol to furnish fluorinated loops. Amphiphilic properties of the latter were investigated by measuring their surface tension and critical micellar concentration CMC. These new amphiphilic compounds may exhibit some interesting interactions with appropriate cations at the surface cells.     

Synthesis and Anti‐HIV Activity of Triazolo‐Fused 3′,5′‐Cyclic Nucleoside Analogues Derived from an Intramolecular Huisgen 1,3‐Dipolar Cycloaddition

Triazolo‐fused 3′,5′‐cyclic nucleoside analogues were synthesized by an intramolecular 1,3‐dipolar cycloaddition of nucleoside‐derived azido‐alkynes in a regio‐ and stereospecific manner. The thymine nucleoside base in these target compounds was transformed successfully into the corresponding 5‐methylcytosine component. The synthesized compounds were examined in a MAGI assay for exploring the anti‐HIV activity and in a H9 T lymphocytes assay for measuring the cell toxicity.     

Discovery of a series of pyridopyrimidine derivatives as potential topoisomerase I inhibitors

A series of new 3-benzoheterocyclic substituted pyridopyrimidines were designed and synthesized. Structures of the compounds were determined by IR, 1H NMR, and elemental analyses. The anti- proliferation activity of 13 novel compounds was evaluated in A549, HL-60, BGC-823 and SMMC-7721 cell lines. Compounds 3, 5, 7, 8, 9,10 showed potent inhibitory activity against the four tested cancer cell lines. These six compounds were examined for Top I inhibition at 100 μmol/L by measuring the relaxation of supercoiled DNA in plasmid pBR322. Most of the tested compounds inhibited the enzyme at this concentration. The most potent compound 9 was as potent as camptothecin.     

CHEMOTHERAPEUTIC POLYMERS. THE SYNTHESIS OF POLYMERS CONTAINING 5-FLUOROURACIL IN THE MAIN CHAIN

1,3-Dialkyl-5-fluorouracil compounds and polymers containing 5-fluorouracil in the main chain were synthesized by the reaction of 5-fluorouracil with alkylbromidcs and polymethylene bromides respectively. The structures of the new compounds and polymers were confirmed by IR and NMR spectra as well as elemental analyses.The factors affecting the polycondensation, such as the temperature and time of the reaction were investigated. The anti-tumor activity of some of the 5-fluorouracil containing compounds and polymers were also measured.