(R)-1,1''''-联萘手性单元通过溶胶凝胶法合成杂化硅干凝胶

0IntroductionSol鄄gel鄄derivedhybridorganic鄄inorganicmateri鄄alsarereceivingmuchattentionsincetheycanexhib鄄itpropertiesassociatedwithboththeorganicmoieties(optical,electrical,molecularimprinting)andinorgan鄄icamorphousframework(porosity,hydrophilicity)[     

1R，3S-1，2，2-三甲基-1，3-环戊二胺为配体的铂(Ⅱ) 配合物的合成、表征和抗肿瘤活性

本文合成了9种含有由天然D(+)-樟脑衍生的1R，3S-1，2，2-三甲基-1，3-环戊二胺(A)为配体的铂(Ⅱ)配合物[Pt(Ⅱ)AX]{其中，X=(CH₂)₃C(COO^-)₂(1，1-环丁烷二羧酸根)，2CH₃OCH₂COO^-，2CH₃CH₂OCH₂COO^-，2CH₃(CH₂)₃OCH₂COO^-，[OCH(CH₃)COO]^2-(乳酸根)，(OCH₂COO)^2-(乙醇酸根)，2CH₃OCH₂CH₂OCH₂COO^-，2CH₃CH₂OCH₂CH₂OCH₂COO^-和2CH₃(CH₂)₃OCH₂CH₂OCH₂COO^-}。通过元素分析、热重分析、红外光谱、¹H核磁共振谱和电喷雾质谱等对配合物进行了表征。体外生物活性测试表明，部分配合物对A549人肺癌细胞和HCT-116人结肠癌细胞具有较强的抗肿瘤活性。     

含多个光学活性联萘和联萘酚配体的合成与不对称加成异构选择性研究

单体(S)-6,6’-二溴-1,1’-联萘酚(S-M-1),(R)-6,6’-二溴-1,1’-联萘酚(R-M-1),(S)-3,3’-二碘-1,1’-联萘酚(S-M-2),(R)-3,3’-二碘-1,1’-联萘酚(R-M-2)分别与(S)-2,2’-二正辛氧基-1,1’-联萘-6,6’-二硼酸(S-M-3), 在钯催化下, 通过Suzuki交叉耦合反应合成手性高分子P-1, P-2, P-3与P-4。归于高分子主链扭曲非平面结构和高分子侧链上引入正辛氧基后使得手性高分子在常规有机溶剂中有较大的溶解性。分析结果表明S-S手性高分子P-1和P-3比旋光值和圆二色谱信号均比S-R手性高分子P-2和P-4要大，但它们紫外和荧光光谱几乎相似。四个手性高分子对二乙基锌与苯甲醛不对称加成异构选择性表明手性高分子不对称催化活性中心是高分子主链中的(S)或(R)-1,1’-联萘酚单元。     

多羟基甾醇25(R)-异螺甾环-5-烯-2β,3α,19-三醇的合成

以薯蓣皂素为原料, 经过磺酰酯化、N-溴代丁二酰亚胺(NBS)氧化加成、Pb(OAc)₄远程氧化关环、消去反应、间氯过氧苯甲酸(mCPBA)氧化、高氯酸开环及锌粉还原7步反应, 合成多羟基甾体25(R)-异螺甾环-5-烯-2β,3α,19-三醇. 并用IR, ¹H NMR, ¹³C NMR, MS及元素分析对各中间体及目标化合物进行了表征.     

硝酸铽与1，1，1′，1′-四(吡啶-2-羧酸酯基)联三甲基丙烷配合物的合成、表征及荧光性质

Solid complex of terbium nitrate with a novel tetrapodal ligand, 1,1,1′,1′-tetra(2-pyridinecarboxylester)-di(trimethylpropane) was prepared. This new complex with the formula of [TbL(NO₃)](NO₃)₂·2H₂O was charact-erized by elemental analysis, molar conductivity, IR spectroscopy and thermal analysis. At the same time, the luminescent property of the complex was also studied.     

N，N′-二甲基-N，N′-二辛基丙二酰胺萃取铀(Ⅵ)的研究

The novel unsymmetrical extractant N，N′-dimethyl-N，N′-dioctylmalonamide (DMDOMA) was prepared by reaction of diethyl malonate with N-methyl octanamine. The extraction mechanism and the behavior of uranyl nitrate with DMDOMA employed cyclohexane as diluent were studied. The effects of concentrations of nitric acid, sodium nitrate, extractant and also the temperature on the extraction were considered. The stoichiometry of the extracted species is and the coordination of extracted species was suggested based on the IR data. The value of ΔH of extraction is -26.9 ± 0.80 kJ·mol^-1. The value of the apparent extraction constant is 133.88 ± 17.92, which shows that the optimization of extractant structure improves the extractability of malonamide for uranyl nitrate.     

二(桥-氯)-二[氯-(N，N，N′-三苄基乙二胺)铜(Ⅱ)]的晶体结构(英)

The crystal structure of the title complex, [Cu(C₂₃H₂₆N₂)Cl₂]₂·2CH₂Cl₂, has been determined by single-crystal, X-ray diffraction techniques. The compound crystallizes as dark-green prisms in space group P2₁/c of the monoclinic system, with Z=4 and unit cell dimensions a=1.710 9(7) nm, b=2.395 2(11) nm, c=1.348 9(6) nm and β=110.651(8)°. The complex consists of two similar but crystallographically independent dimers, of which Cu(Ⅱ) centers display five-coordinated trigonal-bipyramidal geometry with Cu-Cu separations in two centrosymmetric dimers are 0.345 1 and 0.347 8 nm, respectively, and in each dimer the two copper centers share a common edge formed by two bridging chloride ions, each being equatorial. Solvent molecules of CH₂Cl₂ are packed together in the crystal lattice. CCDC: 253299.     

盐酸(R)-沙丁胺醇的不对称合成

研究了一种化学不对称合成盐酸(R)-沙丁胺醇的方法. 以自制的手性龙脑基β-二酮铁络合物为催化剂催化起始原料3-乙酰氧基甲基-4-乙酰氧基苯乙烯(1)的不对称环氧化, 得到(R)-3-乙酰氧基甲基-4-乙酰氧基苯基环氧乙烷(2), 这一步的化学收率和光学收率都较高. 然后环氧化合物2与叔丁胺发生开环反应, 再与盐酸成盐即制得盐酸(R)-沙丁胺醇. 合成盐酸(R)-沙丁胺醇只需两步, 总收率为68%. 还考察了反应温度、催化剂种类、催化剂的量等因素对3-乙酰氧基甲基-4-乙酰氧基苯乙烯(1)的不对称环氧化的化学产率和光学收率的影响.     

手性磺酸基联萘(并冠)醚的合成及水相中直接催化三组分Mannich反应

由1,1'-联-2-萘酚经Williamson合成法及与二甘醇/三甘醇单/双对甲苯磺酸酯反应, 制得10个联萘(并冠)醚, 用氯磺酸磺化, 分别得到10个6,6'二磺酸基联萘(并冠)醚(3a～3f, 6a～6d). 将手性磺酸基联萘(并冠)醚作为Brønsted酸催化剂, 水相中直接催化苯胺、苯甲醛和环己酮三组分Mannich反应, 获得高化学收率(90%～99%)和非对映选择性产物, 其中(R)-6,6'-二磺酸基联萘并-20-冠-6的非对映选择性de 98%. 催化苯胺/取代苯胺、苯甲醛和苯乙酮的反应, 结果显示反应与催化剂和底物分子结构、反应温度及反应时间有关. 催化剂容易回收, 重复使用多次活性基本不减.     

纳米二氧化钛粉末的溶胶-凝胶法合成及晶相转化

Nanosized TiO₂ powder with anatase and rutile structures was synthesized by a sol-gel method using TiCl₄ ethanol solution as a precursor.The grain size of TiO₂ powder was about 63nm after the precursor was calcined at 600℃ for 2 hours .The experimental techniques of XRD,TEM and Particle Distribution were used to characterize the synthesized specimens. Various special effects were investigated for their contribution to crystal structure and the size of TiO₂ powder .The formation of anatase as well as the rutile phase of TiO₂ was indicted from the XRD when the reaction temperature was above 30℃ and when the sol was irradiated by infrared rays .However, an anatase TiO₂ powder formed after the heat treatment of the dried gel in a temperature range from 300℃ to 500℃.Under the vacuum drying and with the calcined time below 3hours ,the anatase phase was gained .As well as with the increase of gelatinizing time, the anatase TiO₂ powder was obtained.     

4,4'',6,6''-四甲氧基-2,2''-二(二苯膦基)-1,1''-联吡啶(P-Phos)铑配合物催化苯乙烯不对称氢甲酰化反应

不对称氢甲酰化反应是以烯烃为原料制备光学活性醛的一种简便有效方法,所获得的光学活性醛则是合成手性药物、农药和食品添加剂等高附加值产物的重要中间体[1],不对称氢甲酰化反应中使用的膦配体在溶液中通常都对氧气非常敏感,少许的氧气就会导致反应活性和对映选择性的大幅降低[2],所以要求实验操作条件非常苛刻。本文报道双膦配体(R) P Phos[4,4’,2’,6,6’ 四甲氧基 2,2’ 二(二苯膦基) 1,1’ 联吡啶]和催化剂前体Rh(acac)(CO)2原位形成的催化剂对苯乙烯不对称氢甲酰化反应的催化性能。考察了反应温度、压力、膦/铑比等对反应的…     

Encapsulation of Organic Pigment Particles with Silica via Sol-Gel Process

This paper presented a novel preparation method of silica coated organic pigment. In this approach, the surfaces of the organic pigment were first orderly modified by poly(sodium 4-styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC), then coated by silica via sol-gel process of tetraethylorthosilicate (TEOS). The results showed that PVP, pH value, water and TEOS contents had significant influence on the morphology of the silica encapsulated organic pigment. Organic pigments coated silica by this approach could scatter UV ray with wavelength less than 270 nm, and this scattering property increased with more silica coated.     

Polyaniline/Silica Hybrid Composite Gels Prepared by the Sol-Gel Process

The preparation of polyaniline/silica hybrid gel was studied by chemical polymerization of aniline with sodium dodecyl sulfate (SDS) during the sol-gel processing. As a typical procedure, aqueous solutions of SDS, aniline, HCl, and tetramethoxysilane (TMOS) were mixed. Then ammonium peroxodisulfate (APS) in an acidic aqueous solution was added as initiator oxidant into the sol-gel systems at different sol-gel stages: (A) just after mixing (sol), (B) after gelation (wet gel), and (C) after 7 d (dried gel). As for the condition (A), several green areas and several tens of dark green spots with absorption peaks at 343, 422, and 802 nm were seen in the xerogel, indicating that emeraldine salt type polyaniline is aggregated in the silica xerogel. Polymerization of aniline little occurred in the dried gel (C), possibly because APS could not soak the silica pores and/or aniline could not polymerize in the gel. The xerogel from (B) showed a homogeneously green color with peaks at 339, 425, and 769 nm, showing that emeraldine salt type polyaniline can be uniformly dispersed in sol-gel silica.     

含(R)或(S)-1,1''''-联萘和噁二唑单元的手性高分子合成与性质研究

在Pd(PPh3)4催化下, 将单体(S)-6,6'-二溴-2,2'-二正丁氧基-1,1'-联萘[(S)-M-1]和(R)-6,6'-二溴-2,2'-二正丁氧基-1,1'-联萘[(R)-M-1]分别与2,5-二(4-三正丁基锡基苯)-1,3,4-噁二唑(M-2)通过Stille交叉耦合反应合成了手性高分子P-1与P-2, 并用 1H NMR、 13C NMR、 FTIR、 UV、热分析、荧光光谱、 GPC和CD等分析方法进行了表征. 手性高分子P-1和P-2都能发射较强的蓝色荧光; 在高分子侧链上引入丁氧基后使得手性高分子的溶解性能增强, 并具有良好的成膜性能; 在高分子主链引入亲电子的噁二唑生色团能使其特别适合于作为空穴电子传输层, 对氧和热特别稳定, 是一类潜在的光电高分子材料.     

Enantioresolution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl oxide using inclusion complex with chiral 2,2'-dihydroxy-1,1'-binaphtyl

An enantioresolution of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl oxide (BINAPO) into its enantiomers was achieved using the inclusion complex with a commerciallyavailable chiral 2,2'-dihydroxy-1,1'-binaphthyl ((R)-BINOL), giving the two enantiomers with 99% ee and 72% ee, respectively.