去氢枞醇杂环类化合物的合成及细胞毒性研究

以去氢枞酸(1)为原料,经氢化铝锂还原得到去氢枞醇(2),2与氯乙酰氯在氮气保护和DMAP催化条件下反应合成中间产物去氢枞醇氯乙酸酯(3),3与杂环化合物经亲核取代反应合成了12个新型去氢枞醇杂环类化合物(4a ～41).利用IR、1H NMR、13C NMR和HR-MS等对目标化合物的结构进行表征,采用MTT法测试目...     

2-取代氨基-5-去氢枞基-1,3,4-噁二唑衍生物的合成及除草活性

以去氢枞酸为原料,经酰化后与水合肼反应合成去氢枞酰肼3,再与芳基异硫氰酸酯反应,得到中间体1-去氢枞酰基-4-取代基氨基硫脲4,4在Hg(OAc)2/EtOH条件下关环,合成得到一系列新型2-取代氨基-5-去氢枞基-1,3,4-噁二唑化合物5.采用IR,MS,1HNMR,13C NMR和元素分析等方法对中间体4和目标产物5进行了分析和表征.初步的除草活性测试表明,化合物4和5对油菜的胚根生长以及对稗草的幼苗生长有一定的抑制作用,其中化合物4d在浓度为100mg/L时对油菜胚根生长的抑制率达88.2％.     

新型去氢枞酸基磺酰胺类化合物的合成及其生物活性

去氢枞酸与SOCl2反应制得去氢枞酸酰氯(2);芳磺酰氯与乙二胺经N-酰化反应制得N-芳磺酰基乙二胺(4a~4k);在DMAP催化下,2分别与4a~4k经N-酰化反应合成了11个新型的去氢枞酸基磺酰胺类化合物(5a~5k),其结构经1H NMR,13C NMR,IR和ESI-MS表征。生物活性测试结果表明,在用药量为50μg·mL-1时,5a~5k对黄瓜枯萎病菌、苹果轮纹病菌、番茄早疫病菌、花生褐斑病菌和小麦赤霉病菌有一定的抑菌活性,其中去氢枞酸基间甲基苯磺酰胺(5c)对番茄早疫病菌的杀菌活性最佳,抑制率为73.6%;在用药量为100μg·mL-1时,大部分化合物对油菜的胚根生长有一定抑制作用,其中去氢枞酸基对甲氧基苯磺酰胺(5d)的抑菌活性最佳,抑菌率为57.1%。     

脂肪族二酸二烷基双去氢枞基双噁二唑的合成及除草活性

以去氢枞酸为原料,制备去氢枞酸酰氯.以脂肪族二酸为原料,经过脂肪族二酸二乙酯得到脂肪族二酸二酰肼.脂肪族二酸二酰肼与去氧枞酸酰氯在相转移催化下反应得到N,N＇-二去氢枞酰基取代脂肪族二酸二酰肼,再脱水环合,得到5个标题化合物脂肪族二酸二烷基双去氢枞基双噁二唑.通过元素分析,IR,MS,1H NMR和13C NMR对所合成的新化合物进行了结构表征.初步的除草活性测试表明,化合物6b～6e在100 μg/mL浓度下对油菜的胚根生长具有良好的抑制作用,抑制率均超过80％.     

ATRP法合成聚去氢枞酸丙烯酸乙二醇酯的研究

本研究从歧化松香中提取的去氢枞酸(DHA)出发,经酰氯化后与丙烯酸(2-羟基)乙酯反应,合成了去氢枞酸丙烯酸乙二醇酯(DHAAGE);并以此为单体,2-溴-异丁酸乙酯(EBr-iB)为引发剂,CuBr/2,2'-联吡啶(2,2'-bipyridine)为催化体系,在90 oC下,利用原子转移聚合(ATRP)法制备了聚去氢枞酸丙烯酸乙二醇酯(PDHAAGE).利用FT-IR、1H-NMR和GPC对所制备的单体和聚合物进行了表征,同时考察了单体转化率随聚合反应时间的变化.结果表明,聚合反应动力学曲线呈良好线性关系,表观聚合速率常数kp′为3.6 ×10-7 s-1;所得聚合物的分子量分布很窄.     

聚去氢枞酸丙烯酸乙二醇酯的合成与表征

从歧化松香中提取的去氢枞酸(DHA)出发,经酰氯化后与丙烯酸(2-羟基)乙酯反应,合成了去氢枞酸丙烯酸乙二醇酯(DHAAGE);并以此为单体,偶氮二异丁腈(AIBN)为引发剂,四氢呋喃为溶剂,在60℃下,利用常规自由基聚合(CPR)法制备了聚去氢枞酸丙烯酸乙二醇酯(PDHAAGE)。考察了单体转化率随聚合时间的变化,并利用FT-IR1、H-NMR、GPC、TG和DSC等对PDHAAGE进行了分析和表征。同时考察了PDHAAGE在不同溶剂中的溶解性。结果表明,得到的PDHAAGE的数均分子量(Mn)约为5400,分子量分布小于1.40;Tg为95.8℃,Tm为375.8℃,热分解温度Td为396.4℃,说明PDHAAGE具有很好的热稳定性;PDHAAGE易溶于中等极性的有机溶剂中。     

2-[1-(1,2,4-三唑)甲基]-3-乙酰基-2,5-二取代芳基-1,3,4-噁二唑啉类化合物的合成

在冰醋酸存在下, 4-取代苯乙酮和溴素容易进行溴代反应, 得到α-溴-4-取代苯乙酮; 将其和1,2,4-三唑在丙酮中反应, 得到α-(1,2,4-三唑-1-基)-4-取代苯乙酮2; 在冰醋酸催化下, 2和4-取代苯甲酰肼1进行缩合, 得到相应酰腙衍生物3; 化合物3在乙酸酐的作用下环化生成一系列2-[1-(1,2,4-三唑)甲基]-3-乙酰基-2,5-二取代芳基-1,3,4-噁二唑啉4. 化合物4的结构经IR, 1H NMR, MS, 元素分析和单晶衍射确证.     

氢键活化的苯环上C-F键的亲核取代反应研究

以2,4,5-三氟苯乙酮在氢化钠作用下与碳酸二乙酯反应制得3,4-二氟-6-乙氧基苯甲酰乙酸乙酯(2);2经对甲基苯磺酸催化水解脱羧,合成3,4-二氟-6-乙氧基苯乙酮(3)路线为模型,研究了苯环上C-F键的亲核取代反应.实验结果证明,在形成分子内氢键的活化作用下,苯环上的C-F键能够被烷氧负离子亲核取代.2和3的结构经1H NMR, 19F NMR和MS表征.     

取代邻羟基苯乙酮的简便绿色合成

以对甲(氯、溴)苯酚(1a-c)为起始原料经酰化得对甲(氯、溴)苯酚乙酯,再以BF3·2HAc为催化剂无溶剂条件下实现Fries重排,以77.3%-80.4%的收率分别得到了5-甲基(氯、溴)邻羟基苯乙酮(2a-c);应用环境友好的聚乙二醇-400为溶剂,N-氯(溴、碘)代丁二酰亚胺为卤代试剂对邻羟基苯乙酮进行卤代反应,以61.8%-92.4%的收率制备3,5-二氯(溴、碘)邻羟基苯乙酮(4a-c);以邻羟基苯乙酮为原料,硝酸铈铵(CAN)为绿色硝化试剂,分别以29.8%和63.9%的收率得到了3位和5位硝化产物1-(2-羟基-3-硝基苯基)乙酮、1-(2-羟基-5-硝基苯基)乙酮(5a-b)。以上制备过程具有反应条件温和、后处理简单、环境友好等优点,为制备取代邻羟基苯乙酮提供了简单且绿色的新方法。     

新型N-杂环取代苯乙酮衍生物的合成

以2-溴-4'-氟苯乙酮(1)为原料,在碳酸钾存在下分别与对甲酚(2a)和邻苯基苯酚(2d)反应制得2-芳氧基苯乙酮化合物(3a和3d);3a和3d分别与咪唑,N-甲基哌嗪和1-(2-嘧啶基)哌嗪经取代反应合成了6个新型的N-杂环取代苯乙酮衍生物,收率63%~81%,其结构经1H NMR,13C NMR,IR和HR-MS表征。     

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.     

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.     

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.     

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.