3-氰基-5-甲氧基苯磺酰氯的合成

3-氰基-5-甲氧基苯磺酰氯是合成多种具有药物活性分子的重要中间体。本文以3,5-二硝基苯甲酸为起始原料,经过取代,酰胺化,脱水,硝基还原,重氮化以及磺化首次合成了目标化合物,其结构经MS和1H NMR确证。该方法原料廉价易得,操作简便易控且收率较高,反应总收率为65.9%。     

含取代基苯基羧酸与柔性含氮配体构筑的三个过渡配位化合物的合成、晶体结构与物理性质（英文）

利用3,5-二硝基苯甲酸(3,5-DNBH),1,2-双咪唑亚甲苯(1,2-bimb)与3种过渡金属盐通过水热反应成功地构筑3个过渡金属配位化合物,即[M(3,5-DNB)2(1,2-bimb)](M=Co(Ⅱ)(1),Cd(Ⅱ)(3))和[Zn(3,5-DNB)2(1,2-bimb)]n(2)。通过红外光谱、元素分析、单晶和粉末X射线衍射表征了这三个化合物。化合物1和3是同构的,含有一个双核单元[M2(COO)2],该双核单元由金属离子、3,5-二硝基苯甲酸根以及1,2-bimb分子构成。双核单元再通过O…π弱相互作用形成超分子结构,该弱相互作用是通过3,5-二硝基苯甲酸根上的硝基氧原子与1,2-bimb上的苯环所形成。化合物2是一维链结构,链与链之间再通过3,5-二硝基苯甲酸根和1,2-双咪唑亚甲苯配体上苯环之间的π…π相互作用,形成了一个超分子结构。室温条件下研究了化合物2和3分散在甲醇中的荧光性质。热重测试结果显示3个化合物具有相对较高的热稳定性。可见光照射条件下化合物1对罗丹明B具有一定的催化降解能力。此外,直流磁化率结果显示化合物1中金属离子之间存在反铁磁相互作用。     

含取代基苯基羧酸与柔性含氮配体构筑的三个过渡配位化合物的合成、晶体结构与物理性质

利用3,5-二硝基苯甲酸（3,5-DNBH）,1,2-双咪唑亚甲苯（1,2-bimb）与3种过渡金属盐通过水热反应成功地构筑3个过渡金属配位化合物,即[M（3,5-DNB）₂（1,2-bimb）]（M=Co（Ⅱ） （1）,Cd（Ⅱ）（3））和[Zn（3,5-DNB）₂（1,2-bimb）]_n （2）。通过红外光谱、元素分析、单晶和粉末X射线衍射表征了这三个化合物。化合物1和3是同构的,含有一个双核单元[M₂（COO）₂],该双核单元由金属离子、3,5-二硝基苯甲酸根以及1,2-bimb分子构成。双核单元再通过O…π弱相互作用形成超分子结构,该弱相互作用是通过3,5-二硝基苯甲酸根上的硝基氧原子与1,2-bimb上的苯环所形成。化合物2是一维链结构,链与链之间再通过3,5-二硝基苯甲酸根和1,2-双咪唑亚甲苯配体上苯环之间的π…π相互作用,形成了一个超分子结构。室温条件下研究了化合物2和3分散在甲醇中的荧光性质。热重测试结果显示3个化合物具有相对较高的热稳定性。可见光照射条件下化合物1对罗丹明B具有一定的催化降解能力。此外,直流磁化率结果显示化合物1中金属离子之间存在反铁磁相互作用。     

新型含寡聚乙二醇链的苄醚树状化合物的合成及其溶液性质

以5-氨基间苯二酚为起始原料,设计并合成了2个新型的含寡聚乙二醇链的苄醚树状化合物———3,5-二-{2-[2-(2-甲氧基-乙氧基)-乙氧基]-乙氧基}-苯氨基甲酸叔丁酯(4)和3,5-二-{3,5-二-{2-[2-(2-甲氧基-乙氧基)-乙氧基]-乙氧基}-苄氧基}-苯氨基甲酸叔丁酯(7),其结构经1H NMR,13C NMR,IR和ESI-HR-MS表征。利用UV-vis光谱研究了4和7的溶液性质,结果表明4和7有热敏感性,其浊点随浓度的增加而降低。     

含取代基苯基羧酸与柔性含氮配体构筑的三个过渡配位化合物的合成、晶体结构与物理性质

利用3,5-二硝基苯甲酸（3,5-DNBH）,1,2-双咪唑亚甲苯（1,2-bimb）与3种过渡金属盐通过水热反应成功地构筑3个过渡金属配位化合物,即[M（3,5-DNB）₂（1,2-bimb）]（M=Co（Ⅱ）（1）,Cd（Ⅱ）（3））和[Zn（3,5-DNB）₂（1,2-bimb）]_n（3）。通过红外光谱、元素分析、单晶和粉末X射线衍射表征了这三个化合物。化合物1和3是同构的,含有一个双核单元[M₂（COO）₂],该双核单元由金属离子、3,5-二硝基苯甲酸根以及1,2-bimb分子构成。双核单元再通过O…π弱相互作用形成超分子结构,该弱相互作用是通过3,5-二硝基苯甲酸根上的硝基氧原子与1,2-bimb上的苯环所形成。化合物2是一维链结构,链与链之间再通过3,5-二硝基苯甲酸根和1,2-双咪唑亚甲苯配体上苯环之间的π…π相互作用,形成了一个超分子结构。室温条件下研究了化合物2和3分散在甲醇中的荧光性质。热重测试结果显示3个化合物具有相对较高的热稳定性。可见光照射条件下化合物1对罗丹明B具有一定的催化降解能力。此外,直流磁化率结果显示化合物1中金属离子之间存在反铁磁相互作用。     

纳米固体超强酸S_2O_8~(2-)/ZrO_2催化合成2-四氢呋喃甲酸冰片酯和2-四氢呋喃甲酸薄荷酯

以冰片、薄荷醇和2-四氢呋喃甲酸为原料,在纳米固体超强酸S2O28-/ZrO2的催化下合成了2-四氢呋喃甲酸冰片酯和2-四氢呋喃甲酸薄荷酯,酯化率分别为67.6%和53.8%,其结构经NMR,IR和元素分析表征。     

纳米固体超强酸S2O2-8/ZrO2催化合成2-四氢呋喃甲酸冰片酯和2-四氢呋喃甲酸薄荷酯

以冰片、薄荷醇和2-四氢呋喃甲酸为原料,在纳米固体超强酸S2O2-8/ZrO2的催化下合成了2-四氢呋喃甲酸冰片酯和2-四氢呋喃甲酸薄荷酯,酯化率分别为67.6%和53.8%,其结构经NMR, IR和元素分析表征.     

四次乙基五胺-环氧氯丙烷阴离子交换树脂的交换速度的测定

本工作测定了四次乙基五胺-环氧氯丙烷阴离子交换树脂对酸的交换吸附速率,包括: 1.用不同配料比合成的树脂,对3,5-二硝基苯甲酸的交换吸附; 2.用一定配料比不同粒度的330对乙酸的交换吸附; 3.用一定配料比的330对数种酸(甲酸、乙酸、己酸、盐酸及3.5-二硝基苯甲酸)的交 换吸附; 4.弱碱330、叔胺化330、季铵化330及强碱201对3,5-二硝基苯甲酸的交换吸附; 5.数种弱碱330对3,5-二硝基苯甲酸的交换吸附。 本文还比较了两种测试交换吸附速度的方法:连续取样法及分批法.实验表明,当被交换吸附的酸浓度若维持在0.032N左右时两种方法所得到的曲线基本上是一致的。     

苯甲酰苯并咪唑衍生物的合成

以3,5-二甲基-1H-吡咯-2-甲酸乙酯(2)为起始原料,与新型Vilsmeier试剂反应得4-甲酰基-3,5-二甲基-1H-吡咯-2-甲酸乙酯(3);3与3,4-二氨基二苯甲酮环合制得4-(5-苯甲酰-1H-苯并咪唑-2-基)-3,5-二甲基-1H-吡咯-2-甲酸乙酯(4);4水解后与2-吡唑啉经脱水反应合成了一个苯并咪唑衍生物,总收率54%,其结构经1H NMR,13C NMR和MS确证。     

新型5-[10-(9-羧基蒽基)]-间苯二甲酸的合成及荧光性质

以5-氨基-间苯二甲酸二甲酯为原料,经重氮化溴取代、Miyaura硼酸酯化反应生成3,5-二甲氧羰基苯硼酸频哪醇酯(3)。此外,以9-蒽甲酸为原料,经溴化、酯化反应生成10-溴-9-蒽甲酸甲酯(6)。最后以化合物3和6为原料,经Suzuki偶联、水解反应得到目标化合物5-[10-(9-羧基蒽基)]-间苯二甲酸。其结构经1H NMR、13C NMR和高分辨质谱表征。研究结果表明,该化合物钠盐水溶液具有发蓝光的性质,最大发射波长为425nm,同时也有较好的荧光量子效率。     

Studies on C-Glycosides XIII C-Glucosides from O-Glucosyl 3,5-Dinitro Benzoate

From O-glucopyranosyl 3,5-dinitro benzoate(1) and aryl ethers C-glucosides were obtained stereoselectively in the presence of Lewis acid in high yield. In most cases, the β-anomer was formed.     

Enhancing effect of borneol on pharmacokinetics of ginsenoside Rb1, ginsenoside Rg1, and notoginsenoside R1 in healthy volunteers after oral administration of compound Danshen dropping pills

Borneol (Bingpian), a monoterpenoid pharmaceutical ingredient, is commonly used as a main composition in traditional Chinese medicine preparations such as compound Danshen dropping pills (CDDP) and has also been approved by the U.S. Food and Drug Administration as a flavoring substance or adjuvant in food. Borneol plays a regulating and guiding role as a messenger drug in CDDP. However, the effect of borneol on the pharmacokinetics of the components of CDDP in human plasma is unclear. In this study, we investigate the effects of borneol on the pharmacokinetics of ginsenoside Rb₁ (Rb₁), ginsenoside Rg₁ (Rg₁), and notoginsenoside R₁ (NR₁) in CDDP. We used a double-cycle crossover-administration model in 12 healthy male volunteers, administered CDDP with borneol (drug T) and without borneol (drug R). The selective response monitoring mode was used for MS quantification in the positive mode. As a result, we found that borneol could significantly affect the pharmacokinetic parameters of notoginsenosides and increase the absorption and systemic exposure of Rb₁, Rg₁, and NR₁ in human plasma by ~1.85–3.71 times.     

毛细管气相色谱法测定驱风苏合丸中冰片的含量

用毛细管气相色谱内标法，不经分离直接测定中成药驱风苏合丸中冰片的含量，有良好的线性关系，相关系数为０．９９９９，７次分析的相对标准偏差，对于异龙脑为０．１３％，对于龙脑为０．３４％。样品处理简单、合理，使用本法于实际样品分析，获得了满意的结果。     

Lipophilicity determination of some 3,5-dinitro-benzoic-acid esters on unimepregnated cellulose layer

Unimpregnated cellulose layers proved to be suitable for the determination of the lipophilic character of 14 3,5-dinitro benzoic acid esters under reversed-phase, thin-layer chromatographic conditions. Lipophilic characters measured on unimpregnated cellulose layers correlated well with similar values determined on impregnated silica and on impregnated alumina. Minor differences in retention of the three types of layers were observed.     

LC Determination of the Intestinal Absorption of Etoposide in Vitro and in Rat Plasma

Etoposide (VP16), an anti-neoplastic agent, exhibits low and variable bioavailability. We have developed and validated a rapid, sensitive, and accurate LC–UV method for the determination of VP16 in vitro and in rat plasma after oral administration. The method was then used to investigate the absorption characteristics of VP16 with an in vitro diffusion chamber system across isolated rat intestinal membranes as a model. Borneol and eugenol were used to enhance the intestinal absorption of VP16. We also examined the effect of borneol and eugenol on the intestinal absorption of VP16 in vivo. The results showed that the plasma concentration of VP16 was significantly increased; relative bioavailability was 2.2-fold and 2.9-fold enhancement in the presence of borneol and eugenol, respectively, compared to VP16 administered alone.     

Synthesis of 4H-[1]benzopyrano[3,4-c][1,2,5]thyadiazol-4-one and its reactions with some nucleophilic and electrophilic agents

The reaction of 3,4-diaminocoumarin with thionyl chloride gave 4H-[1]benzopyrano[3,4-c][1,2,5]thiadiazol-4-one (II), which was cleaved by the action of nucleophilic agents to the corresponding 4-(2-hydroxyphenyl)-1,2,5-thiadiazole-3-carboxylic acid derivatives. The nitration of II leads to the 8-nitro or 6,8-dinitro derivative; the latter was isolated in the form of 4-(2-hydroxy-3,5-dinitrophenyl)-1,2,5-thiadiazole-3-carboxylic acid.See [3] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 977–981, July, 1988.     

LC Determination of the Intestinal Absorption of Etoposide in Vitro and in Rat Plasma

Etoposide (VP16), an anti-neoplastic agent, exhibits low and variable bioavailability. We have developed and validated a rapid, sensitive, and accurate LC–UV method for the determination of VP16 in vitro and in rat plasma after oral administration. The method was then used to investigate the absorption characteristics of VP16 with an in vitro diffusion chamber system across isolated rat intestinal membranes as a model. Borneol and eugenol were used to enhance the intestinal absorption of VP16. We also examined the effect of borneol and eugenol on the intestinal absorption of VP16 in vivo. The results showed that the plasma concentration of VP16 was significantly increased; relative bioavailability was 2.2-fold and 2.9-fold enhancement in the presence of borneol and eugenol, respectively, compared to VP16 administered alone.

     

Enthalpies of formation of 3,4- and 3,5-dinitro-1-trimethyl-1<Emphasis Type="Italic">Н</Emphasis>-pyrazoles

The standard enthalpies of combustion and formation for isomeric polynitropyrazoles, viz., 3,4- and 3,5-dinitro-1-trinitromethyl-1Н-pyrazoles, were measured by combustion calorimetry in an oxygen atmosphere. The enthalpies of formation for the 3,4-dinitro isomer by 19.7 kJ mol^–1 exceeds the corresponding parameter for the 3,5-isomer.     

Synthesis,structural chemistry and antimicrobial activity of −(−) borneol derivative

Borneol is a monoterpene that is a part of traditional Chinese and Japanese medicine. (−) borneol reacted with methanesulfonyl chloride in THF/pyridine to afford the new 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl methane sulfonate derivative in excellent yield. The product is characterized by H1NMR, C¹³NMR, mass spectroscopy as well as elemental analysis and its structure was identified by X-ray single crystal diffraction. The packing of 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl methanesulfonate exhibits the non-classical C-H···O hydrogen bonding in C(4) and R² ₂(8) chain and ring motifs as structural determinants. This was also confirmed by the analysis of Hirshfeld surfaces. The 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl methane sulfonate antimicrobial activity was tested and compared with its parent (−) borneol against three different pathogens. Particularly, 1,7,7-trimethylbicyclo[2.2.1]hept-2-yl methane sulfonate showed high sensitivity, compared to Chloramphenicol reference material, against Escherichia coli.      

In vitro antimicrobial-activity studies on the mixed ligand complexes of Hg(II) with 8-hydroxyquinoline and salicylic acids

A series of mixed ligand complexes of Hg(II) with the general formula Hg (OX) (SA) (where OX: 8-hydroxyquinoline, SA: salicylic, 5-chloro-, 3,5-dibromo, 3,5-diiodo, 3,5-dinitro, acetyl thiosalicylic acids) are isolated in pure state and characterised by elemental analysis and infrared data. The low molar conductance of the complexes in dimethylformamide indicates non-electrolyte nature. The antimicrobial activity of these complexes against various bacteria and fungi is studied which indicates that in several cases, the mixed ligand complexes possess fairly highly antimicrobial activity than the binary mercury-oxinate. The lipophilic tendency of these complexes and its influence on the antimicrobial activity is critically examined. A probable mechanism for the toxic action of these complexes against various organisms is discussed.