含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1,4-二氮革类新化合物的合成(Ⅱ)

设计并合成了2-[1-(4-(N-苯基-N-丙酰基)氨基)哌啶基]甲基-六氢-1H-1,4-二氮 7.由3经还原、氯取代、胺取代、胺脱苄反应得到了7.7经单酰化反应得到了8.8经酰化反应后得到了11个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮类目标化合物(9a～9g,10a～10d).     

甾体-17-酮肟的Beckmann裂解反应研究

研究了甾体-17-酮肟(1a～1i)在PCl5/2,6-二甲基吡啶/CH2Cl2体系中的Beckmann裂解反应.反应得到的烯-腈化合物(2a～2i)是18-去甲基甾体的重要中间体,其结构经1HNMR,IR,MS和元素分析表征.实验结果表明,1的取代基和构型对反应结果没有明显影响.     

含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1，4- 二氮卓类新化合物的合 成(Ⅱ)

设计并合成了2-[1-(4-(N-苯基-N-丙酰基)氨基)哌啶基]甲基-六氢-1H-1,4-二氮卓7.由3经还原、氯取代、胺取代、胺脱苄反应得到了7.7经单酰化反应得到了8.8经酰化反应后得到了11个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮卓类目标化合物(9a～9g,10a～10d)。     

含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1，4- 二氮卓类新化合物的合 成(Ⅱ)

设计并合成了2-[1-(4-(N-苯基-N-丙酰基)氨基)哌啶基]甲基-六氢-1H-1,4-二氮卓7.由3经还原、氯取代、胺取代、胺脱苄反应得到了7.7经单酰化反应得到了8.8经酰化反应后得到了11个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮卓类目标化合物(9a～9g,10a～10d)。     

微波辐射下合成2-(未)取代苯甲酰胺基-5-(1-苯基-3-甲基-5-氯吡唑- 4-基)-1,3,4-噻二唑衍生物

分别在微波辐射和常规加热条件下, 通过2-氨基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑(1)与(未)取代苯甲酰氯(2a～2j)反应, 合成了一系列未见文献报道的2-(未)取代苯甲酰胺基-5-(1-苯基-3-甲基-5-氯吡唑-4-基)-1,3,4-噻二唑衍生物(3a～3j). 标题化合物的结构经元素分析, IR, 1H NMR确证.     

3-(N-取代苯基-2-乙酰胺基)硫基-4-N-取代邻羟苯基亚胺基-5-甲基-1,2,4-三唑类化合物的合成及生物活性研究

以对称二氨基硫脲为原料,与冰醋酸反应生成5-甲基-4-氨基-1,2,4-三唑-3-硫酮(1);在弱酸性条件下,1与取代水杨醛反应生成席夫碱中间体5-甲基-4-(N-取代邻羟苯基)亚胺基-1,2,4-三唑-3-硫酮(2a～2c);最后在碱性条件下分别与N-取代苯基-2-氯乙酰胺发生烷基化反应生成15种未见报道的目标化合物3-(N-取代苯基-2-乙酰胺基)硫基-4-(N-取代邻羟苯基)亚胺基-5-甲基-1,2,4-三唑(3a～3o),其结构经IR,1H NMR,13C NMR确证.初步生物测试表明,质量分数为0.01%时,3a～3o对白色念珠菌的抑菌率均达90%以上,具有很强的抑菌活性;对金黄色葡萄球菌、大肠杆菌的抑菌率达80%以上,具有较强的抑菌活性.     

含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1,4-二氮类新化合物的合成(Ⅰ)

合成了 N,N -二苄基 -2 -甲氧羰基 -六氢 -1 H-1 ,4 -二氮 艹卓 (3 )。 3经还原、氯取代、胺取代、胺脱苄、单酰化及酰化反应后得到了 1 0个带有 (1 -芳乙酰胺基 -2 -叔氨基 )乙烷结构的六氢 -1 H-1 ,4 -二氮 艹卓 类目标化合物 (9a～9i和 1 0 )     

含(1-芳乙酰胺基-2-叔胺基)乙烷结构的六氢-1H-1,4-二氮类新化合物的合成(Ⅰ)

合成了N,N＇-二苄基-2-甲氧羰基-六氢-1H-1,4-二氮 (3).3经还原、氯取代、胺取代、胺脱苄、单酰化及酰化反应后得到了10个带有(1-芳乙酰胺基-2-叔氨基)乙烷结构的六氢-1H-1,4-二氮类目标化合物(9a～9i和10).     

含吡啶环系西佛碱大环配合物和氮杂大环自由配体的合成

2, 6-二羟甲基吡啶(1)经活性MnO~2氧化得到2, 6-二甲酰基吡啶(2)。邻硝基苯酚与N-取代的二(氯乙基)胺在DMF溶液中反应, 得到N-取代的1, 5-二(邻硝基苯氧基)-3-氮杂戊烷(3a～3c), 再经水合肼/Raney Ni还原, 获得N-取代的1, 5-二(邻氨基苯氧基)-3-氮杂戊烷(4a～4c)。利用Ba^2^+作为模板离子, (2)分别与(4a～4c)反应, 合成了一类新的含吡啶环系西佛碱大环配合物I-III, 配合物I、III与NaBH~4的乙醇溶液还原解络, 得到氮杂大环自由配体IV和V。所有西佛碱大环配合物和氮杂大环自由配体均经元素分析、IR、^1H NMR、MS等证实了它们的结构和组成。     

含吡啶环系西佛碱大环配合物和氮杂大环自由配体的合成

2,6-二羟甲基吡啶(1)经活性MnO_2氧化得到2,6-二甲酰基吡啶(2)。邻硝基苯酚与N-取代的二(氯乙基)胺在DMF溶液中反应,得到N-取代的1,5-二(邻硝基苯氧基)-3-氮杂戊烷(3a～3c),再经水合肼/Raney Ni还原,获得N-取代的1,5-二(邻氨基苯氧基)-3-氮杂戊烷(4a～4c)。利用Ba~(2 )作为模板离子,(2)分别与(4a～4c)反应,合成了一类新的含吡啶环系西佛碱大环配合物Ⅰ～Ⅲ,配合物Ⅰ、Ⅲ经与NaBH_4的乙醇溶液还原解络,得到氮杂大环自由配体Ⅳ和Ⅴ。所有西佛碱大环配合物和氮杂大环自由配体均经元素分析、IR、~1H NMR、MS等证实了它们的结构和组成。     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.