5-炔基噁唑啉-2-酮的合成

以廉价易得的取代酸为原料,经取代、硝基还原、氨基磺酰化、炔基格氏试剂加成和羰基化环化反应合成了13个5-炔基噁唑啉-2-酮类化合物,收率为10.6%~71.8%。产物结构经¹H NMR和¹³C NMR确证。      

硫氮杂茚联吡唑的合成及其抗惊厥活性

根据药物设计原理,设计并合成了一系列二甲吡唑-1,3-硫氮杂茚衍生物（6a~6o）,其结构经¹H NMR, ¹³C NMR, IR和MS(EI)表征。采用动物模型验证了6a~6o的活性。结果表明：当取代基为正丁基、正戊基、邻位氟取代苄基和2,6-二氯取代苄基时,化合物表现出较好的抗癫痫活性。其中化合物6g的活性和保护指数均优于阳性对照药丙戊酸钠,并且在MTT实验中未见明显毒性。     

1-氮杂-2,8-二氧杂二环[3.3.0]-辛烷类化合物合成的新方法

以苯基-3,5-二(甲氧基羰基)-2-异(口恶)唑啉-N-氧化物为偶极体,丙烯酸乙酯为亲偶极体,通过[3+2]环加成反应,简便地合成了含有多官能团的1-氮杂-2,8-二氧杂二环[3.3.0]-辛烷类化合物。该反应条件温和,产率较高(50%～93%).化合物的结构经元素分析,¹H NMR,¹³C NMR,IR和MS确认和表证,并对其波谱性质进行了讨论。     

氧杂三螺环化合物的简便合成

以环酮和季戊四醇为原料,磷钨酸为催化剂,在甲苯中回流分水反应合成了系列氧杂三螺环化合物（3a~3h）,其中5,9,14,17-四氧杂三螺［3.2.2.3¹⁰.2⁷.2⁴］十七烷（3a）和7,11,18,21-氧杂-3,15-二硫杂三螺［5.2.2.5¹².2⁹.2⁶］二十一烷（3f）为新化合物,其结构经¹H NMR, ¹³C NMR和HR-MS(ESI)表征。并以3c的合成为模板反应,对反应条件进行了优化。     

1,3-二氢苯并[c]异噻唑2,2-二氧化物的合成工艺改进

1,3-二氢苯并[c]异噻唑2,2-二氧化物是常见的药物骨架，本文以邻氯氯苄和亚硫酸钠为原料，经亲核取代、酰氯化、酰胺化及偶联环化反应，以55%的总收率和99%的纯度合成了1,3-二氢苯并[c]异噻唑2,2-二氧化物，其结构经¹H NMR， ¹³C NMR和FT-IR确证。     

叔胺催化的Sulfa-Michael-Aldol串联反应合成羟基取代的四氢噻吩类化合物

探究了叔胺1,4-二氮杂二环[2.2.2]辛烷(DABCO)催化的2,5-二羟基-1,4-二噻烷和羟基取代查尔酮的sulfa-Michael-aldol串联环化反应。考察了催化剂对反应收率的影响，以最高79%的收率合成了15个多取代的四氢噻吩化合物。 其代表产物的结构经X-ray单晶衍射实验确证，化合物结构经¹H NMR, ¹³C NMR, IR和HR-MS(ESI)表征。      

离子液体1-乙基-3-丁基磺酸咪唑对甲苯磺酸盐催化合成氧杂蒽

以1-乙基咪唑为原料,合成了布朗斯特酸性离子液体--1-乙基-3-丁基磺酸咪唑对甲苯磺酸盐(IL1),并将其用于催化芳香醛与5,5-二甲基-1,3-环己二酮或1,3-环己二酮在无溶剂条件下合成了系列氧杂蒽类化合物,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。研究结果表明：当IL1用量为5 mol%,于80 ℃反应40 min,收率78%~95%; IL1循环使用3次,收率86%~89%,催化活性无明显变化。     

有机-无机骨架杂化酸碱双功能高硅Y型沸石的制备和结构表征

以甲胺水溶液为改性剂, 高硅Y型沸石可在常温下吸附甲胺(MA)制备有机-无机杂化酸碱双功能高硅Y型沸石材料. X 射线粉末衍射(XRD), 固体²⁹Si魔角核磁共振(¹³C及²⁹Si MAS NMR)表征表明甲胺分子与高硅Y型沸石骨架相互作用导致沸石结构发生变化, 骨架上生成新的Si—N键及Si—OH. 以热重分析(TG/DTG), NH₃, CO₂程序升温脱附(NH₃-TPD和CO₂-TPD)研究杂化Y型沸石的酸碱性质及其经不同温度焙烧后的变化, 结果表明, 杂化后沸石的酸/碱量, 尤其是后者明显增大, 其原因是骨架上生成了新的Si—OH及Si—N键.     

4-氨基-N8,N10-二碳杂-N5-取代四氢叶酸类似物的合成及生物活性研究

以2,4-二氨基-6-羟甲基吡啶并[3,2-d]嘧啶为原料,与对甲酰基苯甲酰谷氨酸二乙酯发生Wittig反应构建叶酸类似物的骨架结构,还原吡啶环得到4-氨基-8,10-二碳杂四氢叶酸类似物,在N5位取代不同基团得到四个新的4-氨基-N8,N10-二碳杂四氢叶酸类化合物,经1H NMR,13C NMR和MS对化合物的结构进行了表征.初步生物活性结果表明,此类化合物对人重组胸苷酸合成酶的抑制作用与N5位取代基有关,2个化合物在0.1 μmol·L-1的浓度下对HL-60白血病细胞的抑制率达到60％以上.     

8-三甲基硅乙炔基-6-吡啶-2-基-4H-苯并[f]咪唑并[1,5-a][1,4]二氮杂-3-羧酸乙酯的合成

报道了GABA_A受体的α2/α3选择性配体(HZ-166)的关键中间体8-三甲基硅乙炔基-6-吡啶-2-基-4H-苯并[f]咪唑并[1,5-a][1,4]二氮杂-3-羧酸乙酯(HZ-165)的一种合成方法。该方法以4-溴-2-(2’-吡啶基羰基)苯胺为原料,经亲核加成、关环反应、Vilsmeier-Haack反应和Sonogashira反应合成得到目标产物,产物结构经¹H NMR和MS(ESI)确证。      

Synthesis and Biological Evaluation of Amino Alcohol Containing 1,3,4-Oxadiazole

A series of amino alcohol derivatives containing 1,3,4-oxadiazole moieties was synthesized with 7-bromo-2-tetralone as starting materials, 2,2-dimethyl-1,3-oxazolidine as intermediates and Strecker reaction and cyclization with POCl₃ as key steps. The structures of the key intermediate and target compounds were confirmed by ¹H NMR, ¹³C NMR and HRMS. Some compounds have resulted in the generation of highly potent sphingosine 1-phosphate receptor type 1(S1P₁) agonists.     

Neodymium Complex Obtained from Reductive-coupling of Carbodiimide: Synthesis and Structure of [(Cp")2Nd(NR)2C-C(NR)2Nd(Cp")2]

A bimetallic oxalamidino complex of neodymium [(Cp")₂Nd(NR)₂C-C(NR')₂Nd(Cp")₂][Cp"=η⁵-C₅H₃-1,3-(SiMe₃)₂, R=C₆H₁₁](2) was obtained via reaction between NdI₂ and carbodiimide[RN=C=NR] (R=C₆H₁₁)(molar ratio 1:1) in tetrahydrofuran(THF) solution, followed by the addition of [KCp"(THF)](1)(molar ratio 1:2) at a low temperature through a reductive-coupling reaction with carbodiimide. The structure of the intermediate product was confirmed by means of elemental analysis, ¹H NMR and ¹³C NMR. Characterization of the product by single crystal X-ray diffraction confirmed the diamidinate type of structure.     

D-甘露醇衍生的新型手性硫脲的合成及其在Henry反应中的应用

以D-甘露醇为原料,经缩合,醇解,叠氮化和还原等4步反应制得含联1,3-二氧六环骨架的手性胺中间体(4); 4分别与3,5-双(三氟甲基)苯基异硫氰酯,表奎宁异硫氰酸酯和表奎尼丁异硫氰酸酯偶联合成了3个新型的手性硫脲(6a~6c),其结构经¹H NMR, ¹³C NMR, IR和HR-MS表征。以硝基甲烷和苯甲醛的不对称Henry反应为探针反应,考察了6的催化活性。结果表明：在以吡啶为碱,甲苯为溶剂,6b 5%(摩尔百分数),于-30 ℃反应24 h的条件下,(S)-2-硝基-1-苯基乙醇的收率和对映选择性分别为69%和78%。     

Reaktion von konjugierten doppelbindungsystemen mit dihalogen(diorganylamino)boranen und Na/K-legierung

The reaction of 2,3-dimethylbuta-1,3-diene or 2-methylbuta-1,3-diene with Na/K-alloy and dichloro(diisopropylamino)borane in n-hexane yielded the 1-bora-cyclopent-3-enes, A and II, and 1-bora-cyclonona-1,3-diene, I, respectively. Cycloocta-3,7-diene reacts with dibalogeno(diorganylamino)boranes and Na/K-alloy in n-hexane to yield the 9-bora-bicyclo[4,2,1]non-7-enes III, V, VI and the 1,6-bis(diorganylaminofluoroboryl)-cyclooct-7-enes IV and VH. When 1,2-dimethoxyethane was the solvent, only the dimeric cyclooctene, C, was obtained. The compounds were characterized by elemental analyses and spectroscopy [MS; NMR (¹H, ¹¹B, ¹³C, ¹⁹F)]. An X-ray analysis is presented for I, MNDO-calculations have been carried out for III and III.     

Efficient Synthesis of Beraprost Sodium

An efficient and straightforward synthesis of beraprost sodium was developed with dicyclopentadiene as a starting material, a one-pot reaction product 5 as key intermediate and the Prins reaction and the Horner-Wads- worth-Emmons reaction as key steps. The structures of the key intermediate and the target compound were confirmed by ¹H NMR, ¹³C NMR and MS. The purity of beraprost sodium identified by high performance liquid chromatography(HPLC) was identical to that of Japanese Pharmacopoeia(16^th). This development will be used for the industrial synthesis of beraprost sodium.     

Synthese und Charakterisierung von 1,3-dithia-2-boryl-[3]ferrocenophanen

The 1,3-dithia-2-boryl[3]ferrocenophanes (I-VIII) are obtained from the reaction of ferrocene-1,1′-dithiol (A) with dihalogenorganylboranes by elimination of the hydrogenhalides. I-VIII can be also prepared by starting from Fe(C₅H₄SLi)₂ · 2THF (B) inplace of A, but in lower yields. The air-sensitive [3] ferrocenophanes have been characterized analytically and spectroscopically (MS; NMR: ¹H, ¹¹B, ¹³C).     

2-位氧化糖羰基转位反应的研究

α-甲基－D－葡萄糖苷的2－位羰基衍生物（简称为2－位氧化糖）,不仅在生物体糖代谢过程中起着关键作用,而且由于其自身多个手性中心及高活性羰基的存在,使之成为有机合成中的一种重要手性源,我们在前期的研究中发现,2－位氧化糖的羰基比其它位置氧化的葡萄糖苷具有更高的活性：在D2O中,2－位氧化糖的羰基100％以事形式存在,而3－位氧化糖则100％地以羰基形式存在,4－位氧化糖仅有25％以水合形式存在。因此,2－位氧化糖羰基反应活性的研究在不对称合成中有着重要意义。长期以来此方面的研究主要集中的2－位羰基及其邻位的烷基化,关于其氨基化反应鲜有报道。Tsuda等在合成Nojirimicin的过程中报道了羟胺与2－位氧化糖缩合成肟的反应,我们选择了芳胺与2－位氧化糖的反应进行研究,通过对邻苯二胺与2－位氧化糖反应所形成中间产物的^1H NMR谱变化的跟踪,并选用其它芳胺进行验证,发现芳胺类化合物在与2－位氧化糖反应时,并未生成C＝N双键,而是生成了羰基转化到3－位的加成产物。2－位氧化糖芳胺亲核加成引起羰基转位反应式如Scheme 1所示。     

新型四阳离子型1,2,3-三唑鎓环蕃的合成

以间苯二酚为原料,经5步反应制得中间体4,4′-［4,6-双(己氧基)-1,3亚苯基］双{1-［4-(叠氮甲基)苯基］-1H-1,2,3-三氮唑}(6); 6与1,5-二乙炔基-1,4-二(己氧基)苯在高度稀释的条件下经Click反应环合制得1,2,3-三唑环蕃(7); 7与三甲基氧鎓四氟硼酸盐反应合成了全甲基化的新型1,2,3-三唑鎓环蕃,其结构经¹H NMR, ¹³C NMR和HR-ESI-MS表征。     

Synthesis and thermal properties of novel calix[4]arene derivatives containing 1,2,3-triazole moiety via K2CO3-catalyzed 1,3-dipolar cycloaddition reaction

Two calix[4]arene derivatives containing 1,2,3-triazole moiety were synthesized via K2CO3-catalyzed1,3-dipolar cycloaddition reaction between calix[4]arene-based azide and active methylene compounds in good yields.The structures of the two compounds synthesized herein were fully confirmed by 1HNMR,,（13）C NMR,and MS（ESI）.The thermal analysis showed that the mass losses of the synthesized compounds 4 and 5 containing 1,2,3-triazole groups are similar to each other.     

K3PO4-promoted Cyclopropanation of Electron-deficient Alkenes with 2-Bromo-1,3-propanedione Compounds

An easy and efficient method for the synthesis of multisubstituted cyclopropane derivatives from electron-deficicent alkenes with 2-bromo-1,3-propanedione compounds was described. For this method, ethyl α-cyanocinnamate derivatives 1 and β,β-dicyanostyrene derivatives 4 can all smoothly react with 2-bromo-1,3-propanedione compounds 2 to afford the corresponding multisubstituted cyclopropane derivatives 3 and 5 in good to excellent yields(up to 100%) promoted by anhydrous K₃PO₄ in DMF at room temperature, respectively. A possible mechanism of this reaction was proposed. Structures of all the products were confirmed by ¹H NMR, ¹³C NMR and HRMS.