Stereoselective asymmertric synthesis and characterization of 17α-acetoxy-19-nor-progesterone

17α-actoxy-19-nor-progesterone was synthesized by a new efficient stereoselective asymmertric pathway from 19-nor-androst-4-en-3,17-dione in 5-steps reactions with overall yield 63.3%. Consequently, a strategy was used to produce of 17-α-hydroxyl compound stereoselectively by addition 17-keto steroid with hydrogen cyanide, at the same time, the conditions of this asymmertric reaction were optimized. The titled compound and the intermediate were fully characterized by 1H, one dimension and two dimension 13C-nuclear magnetic resonance, and infrared spectrum. The results show that the rate of 17-α-hydroxyl compound isomeride is sensitively affected by the solution system and the best volume ratio of CH3 OH to H2 O is 36%. After the carbonyl and hydroxyl groups were protected by ethylenediol and vinyl butyl ether respectively, organometallic addition to CN group with CH3 Li, androstance compound was converted to pregnane compound. After removing the protective groups by a mild hydrolytic procedure with high yield, the titled compound was obtained by esterified the above intermidiate. The new pathway gives a good purity of 98% as determined by high performance liquid chromatography.     

苯并[1,2-d:5,4-d']二((口恶)唑)-2,6-二硫醇的合成及表征

苯并(口恶)唑类化合物是一类重要的杂环化合物,不仅在生物、医药等方面有着广泛应用,而且在光学材料、高性能复合材料等诸多领域也显现出独特的性能.以间苯二酚为原料,经过酯化反应和Fries重排、肟化反应、Beckmann重排和水解反应合成4,6-二氨基间苯二酚盐酸盐(DAR· HCl).然后以4,6-二氨基间苯二酚盐酸盐和二硫化碳为原料合成标题化合物,并且优化了过程的工艺条件,过程的总收率为37.3％.利用红外光谱、核磁共振谱、质谱和元素分析等分析手段对中间产物及目标化合物进行了表征.     

2,6-二苯甲酰乙酰基吡啶合成工艺的研究

以吡啶-2,6-二甲酸为起始物,经酯化得到吡啶-2,6-二甲酸二乙酯,然后经过Claisen缩合反应得到了2,6-二苯甲酰乙酰基吡啶。采用元素分析、红外光谱、氢核磁共振谱和质谱对2,6-二苯甲酰乙酰吡啶产物进行了证实,并研究了工艺条件。实验结果表明,在以苯为溶剂,吡啶-2,6-二甲酸二乙酯、苯乙酮与金属钠的摩尔比为1∶4∶4的条件下,把溶解于苯中的苯乙酮滴加到吡啶-2,6-二甲酸二乙酯的苯溶液中进行反应,控制前期反应温度20~25℃,后期反应温度45℃,产物2,6-二苯甲酰乙酰基吡啶的收率可达72.4%。     

黄花菜中黄酮化学成分的测定

以黄花菜为原料,从中提取黄酮化合物,利用荧光法、化学检识法、薄层层析(TLC)定性测定黄花菜中的黄酮化合物的类别。通过其结果可以初步得出黄花菜中提取的黄酮类别为黄酮醇黄酮。     

含磷锌基合金电镀添加剂的研制及模糊评定

合成了一种含磷锌基合金电镀添加剂EA - 1。根据模糊数学的理论 ,利用C语言编程对添加剂的感官指标进行了评定。结果表明 :添加剂EA - 1不仅可以作为镀层中的磷源 ,而且是一种有效的光亮剂。此外 ,该添加剂的评定方法同样适用于其它添加剂的评定。     

有机芳烃类化合物的氧氯化进展

氧化氯化是合成氯代芳香化合物的一条可选途径,可以克服传统路线的副产物多、选择性差等缺点,有利于环境友好型技术路线的开发。文章对芳烃类化合物的氧化氯化的研究进展进行了介绍。     

杂多酸催化合成吡啶-2,6-二甲酸二丁酯

分别以水溶性的杂多酸 H3_PW_(12)O_(40)(PW),不溶性杂多酸盐 H_3PW_(12)O_(40)(PW_(12)),Ce_(0.87)H_(0.4)PW_(12)O_(40),CePW,K_3PW_(12)O_(40)(KPW),(NH4_)4PW_(12)O_(40)(NH_4PW),固载催化剂 PW_(12)/C 等为催化剂对吡啶-2,6-二甲酸的正丁酯化反应进行了研究。发现 H_3PW_(12)O_(40),Ce_(0.87)H_(0.4)PW_(12)O_(40),PW_(12)/C 对本反应有很高的催化活性,其中催化剂 Ce_(0.87)H_(0.4)PW_(12)O_(40)催化活性略小于 H_3PW_(12)O_(40),但因其易回收利用,是本反应合适的催化剂。详细研究了 Ce_(0.87)H_(0.4)PW_(12)O_(40)催化吡啶-2,6-二甲酸的丁酯化反应的工艺条件。当 Ce_(0.87)H_(0.4)PW_(12)O_(40)的用量为5%,醇酸摩尔比为10,反应3h,正丁醇为反应溶剂和带水剂时,吡啶-2,6-二甲酸二丁酯产率达98.2%。经液相色谱测定产物的纯度超过98%,其结构由 IR,~1H-NMR 和~(13)C-NMR 得以表征。催化剂 Ce_(0.87)H_(0.4)PW_(12)O_(40)的重复使用性良好。     

Synthesis and extractive properties of bisthiophosphorylimines

Novel transition metal complexes of bis（diarylsubstitutedthiophosphoryl）imines ligand derived from O,O-di（p-methoxylphenyl）thiophosphoryl chloride and O,O-di-（p-methoxylphenyl）thiophosphoryl amine with Cu（Ⅱ ）,Co（ Ⅱ） ,Ni（ Ⅱ） ,Fe（Ⅱ ） and Mn（ Ⅱ ） were synthesized. The formation mechanism of complexes and their stereochemistry structures were investigated according to elemental analysis,infrared spectra and 31P-nuclear magnetic resonance spectra. The extractions of the ligand for different divalent metal ions,such as Zn（Ⅱ ）,Cd（ Ⅱ） ,Cu（ Ⅱ） ,Ni（ Ⅱ ）,Fe（ Ⅱ） ,Sn（ Ⅱ） ,Mn（ Ⅱ） ,Pd（ Ⅱ） ,Hg（ Ⅱ） and Fe（Ⅲ）,were investigated in sulphate solution,respectively. The results show the metal atom is coordinated by 4 sulfur atoms in a square-planar fashion,and the titled compound has not only powerful ability to coordinate with cadmium from aqueous solution with a high extractive rate about 61.20% and a relatively weak complexation for other divalent metals with the extractive rate from 2.46% to 36.66%,but also a good selectivity to Fe（Ⅲ ）.