乙二胺四乙酸-α,ω-双[2-(2-硝基-1H-咪唑)]乙醇二酯的微波合成

氨基乙醛缩二甲醇和S-甲基异硫脲硫酸盐经缩合和环化反应制得2-氨基咪唑硫酸盐(2);2经重氮化-Sandmeyer后与2-溴乙醇经取代反应制得2-(2-硝基-1H-咪唑)乙醇(4);在微波辐射下,4与乙二胺四乙酸二酐经酯化反应合成了新化合物——乙二胺四乙酸-α,ω-双[2-(2-硝基-1H-咪唑)]乙醇二酯,其结构经1H NMR,FT-IR,HR-MS及元素分析表征。     

(S)-(4-溴-2-甲苯)(3-甲基吗啉)甲酮的合成

以(S)-2-氨基丙醇和氯乙酰氯为起始原料,经酰化和环合反应制得(S)-5-甲基吗啉-3-酮（4）; 4经还原制得(S)-3-甲基吗啉(5); 5与4-溴-2-甲基苯甲酸酰化缩合合成了(S)-(4-溴2-甲基苯基)(3-甲基吗啉)-甲酮,总收率57%,其结构经¹H NMR 和 ¹³C NMR确证。     

1-(3,5-二甲基苯基)-1-[(1S,4S)-1,7,7-三甲基双环[2.2.1]庚烷-2-基]肼的合成工艺改进

以3,5-二甲基苯胺和2-莰酮为起始原料,在微波促进下,经缩合反应制得N-(3,5-二甲基苯基)-1-(1S,4S)-1,7,7-三甲基二环[2.2.1]庚烷-2-亚胺(1);1经硼氢化钠还原后再与羟胺-O-磺酸经胺化反应合成了1-(3,5-二甲基苯基)-1-[(1S,4S)-1,7,7-三甲基双环[2.2.1]庚烷-2-基]肼,总收率70.4%,其结构经1H NMR和ESI-MS确证。     

2-芳基-3,4-二氮杂芴酮和2-芳基-3,4-二氮杂螺二芴衍生物的合成

水合茚三酮与芳甲基酮、水合肼缩合环化制得2-芳基-3,4-二氮杂芴酮(2); 2经还原得2-芳基-3,4-二氮杂芴(3).2与2-溴联苯格氏试剂反应得到中间体叔醇(4); 4在酸性条件下关环合成了2-芳基-3,4-二氮杂螺二芴,其结构经1H NMR,13C NMR和元素分析表征.     

新型含香豆素骨架水杨醛类Schiff碱衍生物的合成

在无溶剂条件下,以草酸为催化剂,间苯二酚与乙酰乙酸乙酯经Pechmann反应制得7-羟基-4-甲基香豆素(1);1经硝化、还原制得3-氨基7-羟基4-甲基香豆素(2);2与取代水杨醛经缩合反应合成了四个新的含香豆素骨架水杨醛类Schiff碱衍生物,其结构经1H NMR,IR和元素分析表征.     

N-丁基-4-[乙基-(3-甲基苯基)氨基]丁酰胺的合成

以γ-丁内酯为起始原料,经开环氯化和酰化反应制得N-丁基-4-氯丁酰胺(2);2与N-乙基间甲苯胺经N-烷基化反应合成了N-丁基-4-[乙基-(3-甲基苯基)氨基]丁酰胺,总收率74.6%,纯度97.6%,其结构经1H NMR和MS(ESI)确证。     

2,2-二丙基-β-丙氨酸的合成

以氰基乙酸乙酯为起始原料,在强碱作用下与溴丙烷经两次烷基化反应制得2-氰基-2-丙基-戊酸乙酯(3);3中氰基经镍催化还原为氨基得2-氨甲基-2-丙基-戊酸乙酯(4);4经水解反应合成了2,2-二丙基-β-丙氨酸,总收率37.4%,其结构经1H NMR确证。     

新型2-甲基吲哚衍生物的合成

2-甲基吲哚在草酰氯的存在下与DMF或DMA通过Vilsmeier-Haack反应制得2-甲基-3-甲酰基吲哚(1)或2-甲基-3-乙酰基吲哚(2);1或2与烷基化试剂通过N-烷基化反应合成了一系列新型的2-甲基吲哚类衍生物,其结构经1HNMR,13C NMR,IR和MS表征。     

(S)-(+)-2,2-二甲基环丙烷甲酰胺的不对称合成

以环己二胺作为手性源,与3,5-二叔丁基水杨醛经缩合反应制得Salen配体(R,R)-N,N'-二(3,5-二叔丁基水杨醛)-1,2-环己二胺(6);甘氨酸乙酯盐酸盐经重氮化和6与三氟甲烷磺酸亚铜催化的不对称环丙烷化反应制得(S)-(+)-2,2-二甲基环丙烷甲酸乙酯(9);9经水解、酰氯化和氨解反应合成了(S)-(+)-2,2-二甲基环丙烷甲酰胺,ee值82%,总收率55.4%,其结构经1H NMR和IR确证。     

3-亚甲基六氢苯并呋喃-2(3H)-酮的简便合成

以氧化环己烯为原料,在正丁基锂作用下与乙腈经开环反应制得2-羟基环己基乙腈(2);2依次经水解、内酯化、二甲胺甲基化、甲基化和Hofmann降解反应合成了α-亚甲基-γ-丁内酯类化合物--3-亚甲基六氢苯并呋喃-2(3H)-酮,总收率30.4%,其结构经¹H NMR,¹³C NMR和HR-MS(EI)确证。     

呫吨类抗胆碱能化合物的合成研究

呫吨羟基羧酸酯类化合物是一类新型高效的抗胆碱、抗梭曼化合物, 比以往的抗胆碱药物效价有较大幅度的提高,设计合成了一系列新的9-羟基-9-呫吨羧酸酯类抗胆碱化合物. 在合成环状基团的过程中, 探索了取代呫吨环中间体的合成路线; 在氨基醇的合成过程中, 采用10%的Pd/C作催化剂, 并将H2的压力下降到30 kg/cm2, 产率提高到90%, 优化了催化氢化的反应条件; 在目标化合物的合成过程中, 改进了产物的纯化和后处理方法, 简化了操作步骤.     

9-羟基-芴-9-羧酸甲酯的晶体结构

9-羟基-芴-9-羧酸衍生物是一种植物生长调节剂。它能引起植物形态变化,还能增强苯氧烷基羧酸类防落素的作用,已广泛应用于名贵花卉和果树等。然而,芴和9-羟基-芴-9-羧酸衍生物的晶体结构均未见报道。本文报告了9-羟基-芴-9-羧酸甲酯的晶体结构。     

9-羟基-9-呫吨羧酸甲酯和中间体的合成

9-羟基-9-咕吨羧酸甲酯是合成咕吨类抗胆碱能药物的一种重要的中间体.本文以9-咕吨羧酸为原料,通过微波催化先合成了中间体9-咕吨羧酸甲酯,然后很简便地得到了9-羟基-9-咕吨羧酸甲酯.在中间体的合成中,利用正交设计,探讨了微波辐射时间、功率以及催化剂用量对反应的影响,实验结果表明微波辐射时间的影响最为显著.     

Expeditious synthesis of 9-allenylpurines via cesium carbonate catalyzed isomerization of 9-alkynylpurines

An expeditious and convenient method to synthesize 9-allenylpurines via cesium carbonate catalyzed isomerization of 9-alkynylpurines has been successfully developed. The reactions proceeded rapidly under the base conditions and formed the desired products in good to excellent yields. The method was suitable with a broad substrate scope and proceeded well even on a multgram-scale. The obtained 9-allenylpurines were successfully applied to prepare various potential bioactive 9-acyclic nucleosides with high regioselectivity promoted by AgNO₃.     

9—羟基—芴—9—羧酸的结构和性质的研究

运用IR、UV及NMR手段研究了9-羟基-芴-9-羧酸的结构,并用MNDO法计算出结构参数,计算结果与其甲基酯的X光晶体结构数据相符.该化合物为由共面性较好的芴环与羟基、羧基构成的不对称分子.     

Thermoelectric Properties of Nano-grained Mooihoekite Cu9Fe9S16

Cu-Fe-S-based compounds gain the interest from thermoelectric community because all the consisting elements, Cu, Fe, and S, are non-toxic and earth-abundant. Comparing with CuFeS₂ and Cu₅FeS₄, the investigation on Cu₉Fe₉S₁₆ is very rare. In this work, a series of Cu_9–xFe_9+xS₁₆ samples were fabricated by means of melting-annealing process. Their phase composition, microstructure, electrical and thermal transport properties were systematically investigated. X-ray measurement confirms that all samples are phase pure. Transmission electron microscopy characterization indicates that the fabricated Cu₉Fe₉S₁₆ has a natural nanostructure. Cu₉Fe₉S₁₆ shows semiconducting-like electrical transport behavior and intrinsically low lattice thermal conductivity. Beyond the numerous boundaries between nanosized grains, the existence of low-frequency optical phonons is also responsible for the intrinsically low lattice thermal conductivity. Doping Fe at the Cu-sites in Cu₉Fe₉S₁₆ significantly alters the electrical transport properties by introducing extra carriers. A peak dimensionless figure of merit zT value of 0.21 is obtained at 800 K for pure Cu₉Fe₉S₁₆, which is comparable with that for CuFeS₂.     

An easy route to exotic 9-epimers of 9-amino-(9-deoxy) cinchona alkaloids with(8S,9R) and(8R,9S)-configurations through two inversions of configuration

Four exotic chiral organocatalysts, 9-amino-（9-deoxy） cinchona alkaloids with （8S, 9R） and （8R, 9S）- configurations, were conveniently synthesized for the first time in 27-72% total yields through two conversions of configuration at the 9-stereogenic centers of commercially available cinchona alkaloids.     

9-氯-9-硼芴与NaBH4反应的理论研究

采用密度泛函理论研究了9-氯-9-硼芴与NaBH₄反应的机理, 优化得到了10个中间体和12个过渡态, 并确定了可能的反应通道. 计算结果表明: 主反应通道包含了6个中间体和5个过渡态, 决速步活化能为80.35 kJ•mol^－1, 9-硼芴并非反应势能面上最稳定的中间体. 解释了实验上不能成功分离出稳定中间体9-硼芴的原因.     

Syntheses of 9-Triptycylisothiocyanate, (10-Amino-9-triptycyl)carboxylic Acid,and Their Derivatives

In the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 9-triptycylisothiocyanate has been synthesized in 91% yield from carbon disulfide and sterically hindered 9-triptycylamine at room temperature. 9-Triptycylisothiocyanate can be further converted to 1-benzyl-3-(9-triptycyl)thiourea. (10-Amino-9-triptycyl)carboxylic acid has also been successfully synthesized via a three-step route starting from methyl 10-nitroanthracene-9-carboylate. Its amino and carboxylic groups can undergo acetylation and amidation, respectively.     

Facile synthesis of 9-(arenethenyl)purines via Heck reaction of 9-vinylpurines and aryl halides

The first example of a Heck reaction with 9-vinylpurines and aryl halides is described. It gives exclusively E-9-(arenethenyl)purines in high yields. Subsequent hydrogenation furnishes 9-(arenethyl)purines quantitatively.