6-氨基己酸的合成与表征——综合性多步有机合成实验

介绍了以环己酮为原料，通过肟化、贝克曼重排和水解开环等3步合成6-氨基己酸的过程，样品经过纯化后，通过1H NMR和13C NMR确证结构。本实验和有机合成课程结合紧密，内容覆盖肟化、重排、水解开环等基本操作，适合作为学生综合实验。     

2-二乙氨基-4-羟基-6-甲基嘧啶的合成

二乙基胍硝酸盐;硝酸盐;BTEA;2-二乙氨基-4-羟基-6-甲基嘧啶的合成     

2-乙酰氨基-3,4,6-三乙酰葡萄糖的合成方法改进

以氨基葡萄糖盐酸盐为原料,在乙酸酐和浓硫酸的作用下合成1,3,4,6-四乙酰基氨基葡萄糖硫酸盐(2)。2在无水醋酸钠和氢氧化钡的作用下进行乙酰基转移反应,合成了2-乙酰氨基-3,4,6-三乙酰葡萄糖。最高收率达84．8％。讨论了乙酰基转移反应的最佳温度和最佳投料比。     

1-氨基-2-萘酚-4-磺酸邻菲啰啉稀土配合物的合成及性质

本文报道了在无水乙醇中合成卜氨基-2-萘酚-4-磺酸、邻菲哕啉与稀土氯化物三元固态配合物的方法。元素分析确定了配合物的化学组成,通过红外光谱、紫外光谱、荧光光谱、~1HNMR谱、热谱、X射线粉末衍射、电学性质、溶解度等手段对配合物进行了表征。     

4-氨基-3,5-二氯-2′-溴苯乙酮的合成研究

溴化铜的溴代反应结果表明：在反应温度为６０℃,原料的摩尔配比为４－氨基－３,５－二氯苯乙酮∶溴化铜＝１∶２,反应２．２ｈ合成标题化合物,溴代产率可达９５％以上     

4-氨基-3,5-二氯-2′-溴苯乙酮的合成研究

溴化铜的溴代反应结果表明：在反应温度为６０℃,原料的摩尔配比为４－氨基－３,５－二氯苯乙酮∶溴化铜＝１∶２,反应２．２ｈ合成标题化合物,溴代产率可达９５％以上     

2-氨基-1,2,3,4,6-O-五乙酰葡萄糖的合成

2 氨基 1,2,3,4,6 O 五乙酰葡萄糖是一种重要的医药中间体,主要是用于合成抗革兰氏阴性菌感染药物类脂A(LipidA)的结构类似物[1,2]。它一般选择盐酸氨基葡萄糖为起始原料,在低温下反应较长时间合成;或者先合成2 氨基 1,3,4,6 O 四乙酰葡萄糖,再乙酰化氨基得到[3,4]。但前者反应时间长,而后者后处理较麻烦。本实验以盐酸氨基葡萄糖和乙酸酐为反应原料,三乙胺为碱,在浓硫酸的催化下,室温下反应较短时间,即可得到目标物乙酰葡萄糖,反应过程采用薄层色谱法(TLC)监控[5]。并应用正交实验设计对影响收率的因素进行了考察。反应路线如下图…     

2-乙酰氨基-3,4,6-三乙酰葡萄糖的合成

细菌内毒素(ＬＰＳ)是革兰氏阳性阴性菌细胞外膜层的主要成分,由其引起的革兰氏阴性杆菌脓度症和休克是导致战创伤病人死亡的主要原因之一。而从类脂Ａ(ＬｉｐｉｄＡ)的结构出发,以非肽类物质拮抗内毒素受体ＣＤ-14为治疗手段的研究在国外刚刚起步。2-乙酰氨基-3,4,6-三乙酰葡萄糖是合成ＬｉｐｉｄＡ结构类似物的重要中间体[1,2]。它的合成一般是通过氨基葡萄糖五乙酸酯的选择性水解[3-6]脱去一个乙酰基得到。氨基葡萄糖五乙酸酯是通过氨基葡萄糖的乙酰化反应得到的,由于氨基葡萄糖不稳定,一般是用氨基葡萄糖的盐酸盐作为起始原料。由于…     

6-取代苯并噻唑-2-氨基硫代磷酸二烷基酯的合成

用6-位取代的2-氨基苯并噻唑与三氯硫磷反应,合成了3个苯并噻唑-2-氨基硫代磷酰二氯,并由此合成了9个苯并噻唑-2-氨基硫代磷酸二烷基酯.讨论了苯并噻唑环上取代基对反应的影响和产物中硫代磷酸酯的烷基的空间效应对反应的影响.所合成的部分化合物对人喉鳞状细胞癌(Hep-2)具有一定的抑制能力.     

新型空间链取代四-(6-氨基己酸磺肽基)铝酞菁配合物的合成及其光物理性质

高锰酸钾降解2-萘酚-6-磺酸钠合成了"分子碎片"4-磺酸钾基邻苯二甲酸(1)。1在钼酸铵催化下,用固相法合成了四-磺酸铝酞菁(2)。采用氨基转化的方法,2经磺酰氯化和Hinsberg磺酰胺化反应分别合成了四-磺酰氯铝酞菁(3)和新型空间链取代四-(6-氨基己酸磺肽基)铝酞菁(4)。1～4结构经1HNMR,IR,MS和元素分析表征,并对4的光物理性质进行了初步研究。     

The hydrogenolysis of C60 and C70

Temperature-programmed reaction (TPR) of C₆₀ and C₇₀ with H₂ was carried out on nickel in order to investigate the thermal stability of the fullerenes in the catalytic hydrogenation. The TPR profiles showed two methanation peaks and the corresponding weight decrease above 420°C, indicating the hydrogenolysis to CH₄. This revised version was published online in June 2006 with corrections to the Cover Date.     

C60Co(Pph3)2的合成和表征

The fullerene complexe C₆₀Co(Pph₃)₂ has been prepared by the reaction of C₆₀ with CoCl₂(Pph₃)₂ under a nitrogen atmosphere and refluxing， and characterized by elemental analyses， FT-IR， XPS， NMR， which appove that C₆₀ coordinates to Co(Pph₃)₂ group in σ-π pattern and the electron is super conjugate over whole molecule. The result of redox property study show that the reduction potentiel of C₆₀Co(Pph₃)₂ is more negative than that of C₆₀， the reason may be the π electron dentensity of C₆₀ in C₆₀Co(Pph₃)₂ increases， which lead to it′s electron affinity decreasing. The thermostability experiment indicates that the oxidation decomposition temperature of C₆₀Co(Pph₃)₂ is lower than that of pure C₆₀.     

Hydrothermal Synthesis and Crystal Structure of a New 2D Zinc（Ⅱ） Coordination Polymer with 2-Aminoethanesulfonic Acid

A new 2D Zn(Ⅱ) coordination polymer [Zn(TAU)2]n (1, HTAU=2-aminoethane- sulfonic acid) constructed by 2-aminoethanesulfonic acid ligand has been hydrothermally synthesized by the reaction of Zn(CH3COO)2 and 2-aminoethanesulfonic acid with a 1:2 mole ratio and characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. Crystal structural analysis reveals it crystallizes in monoclinic, space group P21/c with a=8.672(4), b=6.523(3), c=9.134(5) , β=115.441(5)°, V=466.6(4) 3, Mr=313.65, Z=2, Dc=2.232 Mg·m-3, F(000) =320, μ(MoKα)=3.091 mm-1, the final R=0.0358 and wR=0.0919 for 2026 observed reflections with Ⅰ > 2σ(Ⅰ). In the structure, each zinc(Ⅱ) ion is coordinated in a slightly distorted octahedron, and each μ3-TAU– acts as a bridge to bond three neighboring Zn(Ⅱ) ions to form an infinite 2D network structure.     

C60RuH2(CO)(PPh3)配合物的合成和氧化还原性能研究

自从1985年Kroto等人发现C60等碳原子簇以来,在化学、物理以及材料科学掀起了富勒烯的研究热潮。目前富勒烯配合物的制备及其性质的研究是富勒烯化学最为活跃的研究领域之一,人们正致力于探索富勒烯各类衍生物的结构与性质之间的依赖关系,以期合成出具有特殊性能的富勒烯配合物,为富勒烯的实际开发应用奠定基础。本文合成表征了C60RuH2(OH)(PPh3)配合物,研究了其氧化还原特性。     

Synthesis of water-soluble C60 derivatives and their scavenging free radical activity

Four piperazine-appended [60] fullerenes (1a-1d) were synthesized and characterized. Their activities of scavenging radical were studied via UV-Vis and EPR. The results indicate that light irradiation is of advantage to increase the activity of scavenging radical.     

Semiempirical molecular dynamics studies of C60/C70 fullerene oxides: C60O, C60O2 and C70O

The spectral analysis indicates that all isomers of C₆₀O, C₇₀O and C₆₀O₂ have an epoxide-like structure (an oxygen atom bridging across a C–C bond). According to the geometrical structure analysis, there are two isomers of fullerene monoxide C₆₀O (the 5,6 bond and the 6,6 bond), eight isomers of fullerene monoxide C₇₀O and eight isomers of fullerene dioxide C₆₀O₂. In order to simulate the real reaction conditions at 300 K, the calculation of the different isomers of C₆₀O, C₆₀O₂ and C₇₀O fullerene oxides was carried out using the semiempirical molecular dynamics method with two different approaches: (a) consideration of the geometries and thermodynamic stabilities, and (b) consideration of the ozonolysis mechanism. According to the semiempirical molecular dynamic calculation analysis, the probable product of this ozonolysis reaction is C₆₀O with oxygen bridging over the 6–6 bond (C_2v). The most probable product in this reaction contains oxygen bridging across in the upper part of C₇₀ (6–6 bond in C₇₀O-2 or C₇₀O-4) an epoxide-like structure. C₆₀O₂-1, C₆₀O₂-3 and C₆₀O₂-5 are the most probable products for the fullerene dioxides. All of these reaction products are consistent with the experimental results. It is confirmed that the calculation results with the semiempirical molecular dynamics method are close to the experimental work. The semiempirical molecular dynamics method can offer both the reaction temperature effect by molecular dynamics and electronic structure, dipole moment by quantum chemistry calculation.     

富勒烯配合物C60Pd(Ph2PCH2CH2CH2CH2PPh2)的合成和光电性能

本文在惰性气氛中通过取代反应合成出富勒烯金属配合物C₆₀Pd(Ph₂PCH₂CH₂CH₂CH₂PPh₂)，采用元素分析、红外光谱、紫外可见光谱、光电子能谱以及X射线粉末衍射等手段对产物进行表征,同时研究了产物的氧化还原性能及热稳定性能。此外，在光电化学电池中测定了C₆₀Pd(Ph₂PCH₂CH₂CH₂CH₂PPh₂)在GaAs电极上形成n+n型异质结的光伏效应，结果表明：产物具有优良的光电转化性能，尤其是在BQ/H2Q介质电对中，光生电压最大达到212 mV；当C₆₀Pd(Ph₂PCH₂CH₂CH₂CH₂PPh₂)薄膜厚度为1 μm时，光伏效应值最大。     

Dipole polarizability pseudospectra and C6 dispersion coefficients for H2–H2

Pseudostate decomposition of static dipole polarizabilities for ground state H₂⁺ from a Givens-Householder diagonalization of the excitation operator (

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H" height="17" width="20">₀−E₀) over an N-term basis of appropriate symmetry allows for a rapidly convergent evaluation of C₆ dispersion coefficients for H₂⁺–H₂⁺. 27-term pseudospectra of hypergeneralized James functions with a 30-term GGJ⁺ unperturbed wavefunction with an optimized scale factor δ=0.918 at R=2₀ give C₆ and γ₆ values that are accurate to no less than nine significant figures.     

Catalytic hydrogenation of C60 on transition metals

The catalytic hydrogenation of C₆₀ on Ru, Rh and Ir produced C₆₀H₁₈ mainly, while Pd, Pt, Co and Ni catalysts gave C₆₀H₃₆ principally. Very little activity was observed on Au and Fe. The higher hydrogenated fullerene obtained on Pd, Pt, Co and Ni was ascribed to the smaller % d-character of the metallic bond, on which the fullerene and hydrogen may more strongly be adsorbed. This revised version was published online in August 2006 with corrections to the Cover Date.