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(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).     

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)。     

含（1—芳乙酰胺基—2—叔胺基）乙烷结构的六氢—1H—1，4—二氮Zhuo类化合物的合成与镇痛活性

2－或－5－取代的六氢－1H－1，4－二氮Zhuo类化合物（1－3）经单酰化及酰化反应后，合成了16个带有（1－芳乙酰胺基－2－叔胺基）乙烷结构的六氢－1H，1－4二氮Zhuo类目标化合物（5－9，11－13，15－17，19－23），经元素分析，IR，MS和^1H NMR确证了其组成和结构。对所有目标化合物都进行了豚鼠回肠试验，初步药理试验表明，16个化合物对受试标本显示不同程度的抑制作用，对抑制率较高的两个化合物和5和7测试了IC50值。对在豚鼠肠试验中显示较强激动作用的4个化合物进行了小鼠扭体法镇痛活性试验，测得了其ED50值。     

含1,2,3-三氮唑结构的1,5-苯并硫氮杂[艹卓]的合成及其抑真菌活性

设计合成了三类含1,2,3-三氮唑结构的1,5-苯并硫氮杂[艹卓]化合物3-(1H-1,2,3-三氮唑)-4-芳基-2,5-二氢-1,5-苯并硫氮杂[艹卓](5a^5f)、3-(2H-1,2,3-三氮唑)-4-芳基-2,3-二氢-1,5-苯并硫氮杂[艹卓](6a^6f)和3-(1H-1,2,3-三氮唑)-4-芳基-2,3,4,5-四氢-1,5-苯并硫氮杂[艹卓](7a^7f).研究了中间体及目标产物的合成条件,分离出其中两个副产物并进行了结构确定.目标产物的抑真菌活性测试表明,化合物5a^5f对真菌具有良好的抑制作用,对新生隐球菌的抑制效果尤为突出.初步抑真菌构效关系研究表明, 1H-1,2,3-三氮唑环和C=C双键是化合物5a^5f抑真菌活性的关键官能团.     

2,3,4,5-四氢-1,5-甲桥-1H-3-苯并氮杂(艹卓)的合成

以1,4-二氢-1,4-甲桥萘为起始原料,经臭氧化、还原性胺化及还原反应合成了新型戒烟药伐仑克林的重要中间体2,3,4,5-四氢-1,5-甲桥-1H-3-苯并氮杂(艹卓),其结构经1H NMR和MS确证.     

2-芳胺基-3H-1,3,4-噻二唑-5-硫醇类介离子化合物的X射线光电子能谱研究

用XPS表征2-芳胺基-1,3,4-噻二唑-5-硫酮(1)在ω-溴代-ω-(1H-1,2,4-三唑)-苯乙酮诱导下生成的2-芳胺基-3H-1,3,4-噻二唑-5-硫醇类介离子化合物(4).结果表明,化合物4分子中的C_1s,N_1s,S_2p电子结合能均高于化合物1,尤其以N_1s,S_2p结合能谱最为特征.例如在含3个氮原子的化合物4中由于噻二唑环的两个氮环境不同,故产生3个峰,而在与其结构相近的对照物1中,由于噻二唑环的两个氮环境相近,故产生2个峰.S_2p诸状态结合能加合值化合物4均大于化合物1,在化合物4中均是杂环内硫大于杂环外硫.     

一个取代的三环1,5-苯并二氮杂(艹卓)的晶体结构和构象分析.Ⅱ

用单晶X射线衍射方法测定了6-苯甲酰基-5-(邻氯苯基)-2,3,3a,4,5,6-六氢-3a-苯基-(1,2,3-三乙酸乙酯基)-1H-吡咯啉[1,2-a][1,5-]苯并二氮杂(艹卓)的晶体结构.单斜晶系,空间群P21/c,a=1.3235(5)nm,b=1.7142(6)nm,c=1.6204(6)nm,β=100.49(3)埃琙=4,最终偏离因子R=0.062,Rw=0.075.晶体结构测定结果表明分子中二氮杂(艹卓)七元环采取船式构象,动力学模拟退火计算结果的最低能量构象为椅式,两者的能量差不大,表明这种船式←→椅式的变化是非常容易发生的.     

Synthesis of 5-Substituted Hexahydro-1H-1, 4-Diazepine Analogues

Searching for new analgesic is still of great interesting for the researchers. Opioids have been a hot topic for their powerful pain relieving properties and their potential for recreational abuse1,2. In the previous paper3 we have reported the synthesis of 2- substituted hexahydro-1H-1, 4-diazepine analogues. In order to get more selective k-opioid receptor agonists, which can elicit ana lgesia while lacking serious side effects, a series of 5-substituted hexahydro-1H-1, 4-diazepine analo…     

Synthesis of 2-Substituted Hexahydro-1H-1,4-diazepine Analogues

Opioids have attracted increasing research interest, primarily because of their powerful pain relieving properties and their potential for recreational abuse1,2. In order to get some selectiveκ-opioid receptor agonists, which can elicit analgesia while lacking serious side effects, a series of hexahydro-1H-1,4-diazepine analogues carrying the segment of (1-arylacetamide-2-tertiaryamine) ethane have been synthesized in our laboratory. The κ-opioid receptor antagonistic activity3of these compo…     

1-羟基异喹啉及羟基Fasudil的合成

首先以异喹啉为原料,经氧化生成氮氧化物后与苯甲酰氯和水作用,得到1-羟基异喹啉,收率为73.3%.以Fasudil为原料,经氨基保护、氧化,在相转移催化剂的存在下,于二氯甲烷和水的两相体系中与苯甲酰氯和水作用,合成羟基Fasudil,HPLC纯度大于99%,总收率为46.8%,从而建立了一条条件温和、操作简便的羟基Fasudil的合成工艺路线.     

Asymmetric synthesis of (R)-6-amino-1-methyl-4-(3-methyl-benzyl)hexahydro-1H-1,4-diazepine from L-asparagine

An efficient asymmetric synthesis of (R)-6-amino-1-methyl-4-(3-rnethylbenzyl)hexahydro-1H-1,4-diazepine [(R)-2] which serves as the amine part of (R)-1, a potent and selective 5-HT₃ receptor antagonist, is described. Formation of the hexahydro-1H-1,4-diazepine ring was achieved by the intramolecular ami-dation of the optically active aminocarboxylic acid 18 or reductive cyclization of the optically active aminoaldehyde 25. Compounds 18 and 25 were prepared from L-asparagine via the key aziridine derivatives 15 and 22 , respectively, with retention of the configuration. The intramolecular aziridine ring opening reaction of 29 gave the C₂? N bond cleavage product of the aziridine ring, the piperazin-5-one 30 , as the main product along with the desired 7-membered ring, the hexahydro-1H-1,4-diazepine product 19 .     

Synthesis and Thermodynamic Properties of M2L[M=Li,Na; L=3,6-Bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine]

Two novel energetic alkalic metal salts of 3,6-bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz), Li₂(BTATz)·6H₂O(compound 1) and Na₂(BTATz)·2H₂O(compound 2), have been synthesized by the reaction of BTATz with lithium hydroxide or sodium hydroxide in dimethylsulfoxide(DMSO) solution, respectively, and their structures were characterized by means of elemental analysis and Fourier transform infrared spectrometry(FTIR). Moreover, the single-crystal structure of compound 1 was determined by single crystal X-ray diffraction. It crystallizes in the monoclinic space group P1/c. Furthermore, their thermal decomposition behaviors were investigated by means of differential scanning calorimetry(DSC) and thermogravimetry-differential thermal gravimetry(TG-DTG). The results show that the exothermic decomposition peak temperatures for compounds 1 and 2 were 642.65 and 644.46 K, respectively, and the kinetic equations of the main exothermic decomposition were also derived from non-isothermal method. Additionally, the thermal safety of the two compounds was evaluated by calculating self-accelerating decomposition temperature(T_SADT) and critical temperature of thermal explosion(T_b). The results(the T_SADT and T_b values are 605.43 and 635.69 K for compound 1; 607.38 and 638.96 K for compound 2) reveal that the two compounds exhibit better thermal safety than BTATz.     

柳叶五层龙正丁醇提取部分中的3个新酚性成分及其α-葡萄糖苷酶抑制活性

采用多种色谱分离方法从柳叶五层龙(Salacia cochinchinensis Lour)的茎叶中分离得到5个化合物. 通过一维(1D)及二维核磁共振波谱(2D NMR), 包括核磁共振氢谱(¹H NMR)、 核磁共振碳谱(¹³C NMR)、 异核单量子相关(HSQC)、 异核多键相关(HMBC)、 氢氢相关(¹H-¹H COSY)和旋转坐标中的欧沃豪斯增强光谱(ROESY), 以及红外光谱(IR)和电喷雾电离高分辨质谱(ESI-HRMS)等方法, 鉴定其结构分别为Salaciacochinoside A(1), 5'-O-3,4,5-trimethoxybenzoyl-β-D-apiofuranoside(2), 5-methoxy-anticerol A(3), 21α,30-dihydroxy-D∶A-friedooleanan-3-one(4)和21α,26-dihydroxyfriedelan-3-one(5). 化合物1~3为新化合物. α-葡萄糖苷酶抑制活性测试结果显示, 化合物1和3对α-葡萄糖苷酶具有显著的抑制作用, 其IC₅₀值分别为0.32和0.59 μmol/L; 化合物2, 4和5未表现出α-葡萄糖苷酶抑制活性.     

Synthesis and Thermal Properties of Three Energetic Ion Salts of 3,6-Bis[(1H-1,2,3,4-tetrazol-5-yl)-amino]-1,2,4,5-tetrazine

Three energetic ion salts of 3,6-bis[(1H-1,2,3,4-tetrazol-5-yl)-amino]-1,2,4,5-tetrazine(BTATz), namely, methylamine salt(compound 1), ethylenediamine salt(compound 2), and diethylamine salt(compound 3), were synthesized and characterized by elemental analysis, Fourier transform infrared spectrometry, NMR spectroscopy, and ^13C NMR spectroscopy. The crystal structure of compound 1 was determined by single-crystal X-ray crystallography, and structural analysis revealed that it belonged to the monoclinic system with P21/c space group. In addition, the thermal behavior of the three compounds was studied by differential scanning calorimetry and thermogravimetry techniques. The thermal decomposition peak temperatures of the compounds were 574.89, 545.60, and 606.72 K, indicating that the three ion salts exhibited good thermal stability. Tlie kinetic mechanism equations of the main decomposition process and the entropy of activation(△S^≠), enthalpy of activation(△H^≠), and Gibbs free energy of activation(△G^≠) of the three compounds were also obtained. Moreover, the thermal safety of the compounds was evaluated by the values of the self^accelerated decomposition temperature(Tsadt)5 thermal ignition temperature(TTIT), and critical temperature of thermal explosion(7b). The results showed that all the compounds demonstrated good thermal safety, and the thermal safety of compound 3 was better than that of the others.     

Efficient synthesis and in vitro antifungal activity of 1H-benzimidazol-l-yl acetates/propionates containing 1H-1,2,4-triazole moiety

A series of novel 1H-benzimidazol-1-yl acetates and 1H -benzimidazol-1-yl propionates containing 1H-1,2,4-triazole moiety were synthesized under microwave irradiation by multi-step reactions,in yields of 87-94%.Their in vitro antifungal activities against Botrytis cinerea and Sclerotinia sclerotiorum were evaluated by mycelial growth rate method.All the target compounds exhibit high activities against B.cinerea with the EC₅₀ values of 7.96-21.74μg/mL,higher than that of carbendazim.