聚酰胺-胺-2-吡啶甲醛席夫碱树枝状大分子钯配合物的制备、表征及催化性能

制备了聚酰胺-胺(PAMAM)-2-吡啶甲醛(Py)席夫碱树枝状大分子及其钯配合物。通过红外、核磁共振、元素分析、等离子耦合原子发散光谱及热重-差热等分析手段对其进行了结构确证。研究了PAMAM-2-吡啶甲醛席夫碱钯配合物在Heck反应中的催化性能。以三乙胺(Et₃N)作为缚酸剂,碘代苯(PhI):10 mmol,n(PhI):n(AA):n(Et₃N)为1:1.4:2.5,n(Pd)=6.1×10^-3 mmol(5.0G PAMAMPy-Pd),在5 mL DMF中,100 ℃和N₂气保护下反应25 min,产率90.1%。催化剂经过简单的过滤可回收,重复使用3次产率仍可达82.0%。     

(聚酰胺-胺树枝状大分子)-水杨醛席夫碱钯配合物的Heck反应催化性能研究(英文)

用元素分析、红外光谱、紫外光谱、荧光光谱和核磁等分析手段对合成出的1.0G树枝状大分子-水杨醛席夫碱钯配合物(PAMAMSAPd)进行了表征。用其作为催化剂,研究了碘代苯与丙烯酸在有机溶剂中的偶联反应。对于碘代苯与丙烯酸的偶联反应,最佳反应条件为:惰性气氛,10mmol PhI,nPhI∶nAA∶nEt3N=1∶1.5∶2.5,3.0×10-3g PAMAMSAPd, 4mL DMF和100°C的反应温度。在该条件下,产物肉桂酸的产率可达96.5%。该树枝状大分子配合物是一种无磷、高效和稳定的Heck反应催化剂。且该催化剂经简单的过滤、溶剂洗涤进行回收,重复使用3次,产率仍能达到90.2%。     

乙二胺四乙酸为核的新型树枝状聚酰胺-胺的合成

采用扩散法,以乙二胺四乙酸为起始核,乙二胺和甲基丙烯酸甲酯(MMA)为原料,经重复酰胺化和Michael加成反应合成了一系列新型的树枝状聚酰胺-胺大分子(G0.5,G1.0和G1.5),其结构经1H NMR和IR表征。合成G0.5和G1.5的最佳原料配比分别为1∶24和1∶40。合成G1.0的最佳反应条件为:G0.5 12.829mmol,n(G0.5)∶n(MMA)=1∶16,于40℃反应24 h,产率85.7%。     

一代碳硅烷树枝状大分子钯配合物的液晶性

合成了新的周边含12个4-硝基偶氮苯端基一代碳硅烷树枝状大分子的钯(II)配合物(G1Pd), 并用元素分析、核磁共振氢谱、碳谱、红外、紫外-可见光谱、能量色散X射线分析(EDXRA)、偏光显微镜、差示扫描量热法和广角X射线衍射法对其结构和液晶性质进行了表征. 配合物G1Pd的相行为是K122ch189I166ch90K. 给出一种具有新的结构特点的液晶性树枝状大分子, 它兼有配位金属和介晶基元. 在液晶和液晶高分子界观察到首例胆甾相的高强向错和首例树枝状大分子配合物的高强向错现象.     

树枝状吡啶亚胺铬催化剂的合成及其催化性能研究

以1. 0代聚酰胺-胺树枝状大分子为配体骨架、吡啶二甲醛为原料,合成了一种新型树枝状吡啶亚胺(DPI)配体,再以CrCl_3·6H_2O为络合试剂,制备DPI-Cr催化剂。采用IR、UV-Vis、MS、元素分析等确证了产物结构。考察溶剂种类、助催化剂种类、反应温度、乙烯压力以及Al/Cr摩尔比对DPI-Cr催化乙烯齐聚性能的影响。结果表明,DPI-Cr催化剂表现出良好的催化活性和烯烃选择性,优化反应条件下,催化效率可达4. 91×10~4g/mol Cr·h,C_6和C_8选择性为73. 90%。     

双齿氮配体钯配合物催化的羰化反应研究

研究了双齿氮配体钯（II）配合物催化剂（1-3）在对邻溴碘苯与胺的羰化合成酰胺反应以及炔烃的氧化羰化制备炔酸酯反应中的催化性能,考察了不同条件下催化剂的催化活性并对其反应产物进行了表征.研究结果表明该催化剂在酰胺化合成氮取代邻苯二甲酰亚胺的反应中表现出了较好的催化活性和选择性,分离收率和选择性高达88%和85%;在芳基...     

高纯度树状大分子聚酰胺-胺的合成与表征

以乙二胺为核,通过Michael加成,与丙烯酸甲酯交替反应,合成了0.5代到5.0代聚酰胺 胺树状大分子。 利用傅里叶变换红外光谱、核磁共振氢谱、液相色谱和元素分析等对各代产品进行了表征,探索了反应温度、时间及反应物配比对产物的影响,确定生成聚酰胺-胺(PAMAM)的半代产物时反应温度为25 ℃,整代产物时反应温度为35 ℃;0.5G的反应时间为18 h,1.0G、1.5G的反应时间为24 h,2.0G、2.5G反应36 h,3.0G、3.5G反应48 h,4.0G、4.5G反应3 d,5.0G反应4 d。 分离提纯是树状大分子制备中遇到的最大困难,通过选择性溶剂萃取的方法对产品分离纯化,筛选出乙醚作萃取剂、甲醇作溶剂交换剂,大大提高了产品的纯度。     

微波辅助合成聚酰胺-胺修饰硅胶及其对牛血清白蛋白的吸附性能研究

采用微波辅助合成法制备了聚酰胺-胺树枝状大分子修饰硅胶,并考察了其对牛血清白蛋白(BSA)的吸附性能。PAMAM修饰硅胶的合成条件通过元素分析进行考察,不同代数PAMAM修饰硅胶通过傅里叶变换红外光谱法表征。结果表明,在微波辅助下制备的PAMAM修饰硅胶的红外光谱图中出现酰胺的特征吸收峰与采用传统加热方法的文献报道一致,而采用微波辅助和传统加热方法的反应时间分别为40min和24h,由此说明微波辅助合成聚酰胺-胺树枝状大分子修饰硅胶是可行的。同时研究还发现聚酰胺-胺修饰硅胶对蛋白的吸附能力比未经修饰的硅胶强,而且蛋白的吸附量随着聚酰胺-胺代数的增加而增加。     

1,4-二烯和醛的烯丙基碳氢不对称烷基化反应

利用钯配合物、有机胺和手性布朗斯特酸三元催化剂体系实现了α-取代丙醛参与的1,4-二烯烃的烯丙基碳氢不对称烷基化反应,以良好的产率、优良的区域选择性和立体选择性得到了结构多样的手性α-羰基化合物.此外发现非手性膦配体对钯配合物的催化活性和反应的选择性有十分显著的影响,为后续相关研究提供了新的思路.     

树枝状钴系催化剂的合成及催化乙烯齐聚性能

以1,8-辛二胺为核的1.0代(1.0G)树枝状大分子、水杨醛和六水氯化钴为原料,依次通过席夫碱反应和配位反应合成了一种新型的树枝状水杨醛亚胺配体和钴系催化剂;并对目标产物进行FT-IR、UV、1H NMR和MS表征,证实其合成产物的结构与理论结构相符。考察了助催化剂种类、溶剂种类、反应条件及金属活性中心对乙烯齐聚性能的影响。结果表明,当以一氯二乙基铝(Et2AlCl)为助催化剂,甲苯为溶剂时,催化剂具有良好的催化乙烯齐聚性能,并在反应温度为25℃、Al/Co摩尔比为1500、压力为1.0 MPa、时间为0.5 h时,催化活性达到6.84×105 g/(mol Co?h),齐聚产物中C8及C8以上的烯烃含量为52.77%。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.