某些氰基甲(月无无日)类试剂与表面活性剂的作用机理

本文研究了表面活性剂对1,5-二(2-羟基-5-氯苯基)-3-氰基甲(月朁)(HCPCF)及1,5-二(2-羟基-5-磺基苯基)-3-氰基甲(月朁)(HSPCF)以及其金属络合物吸收光谱的影响;通过对电泳、析相等现象的分析,探讨了HCPCF、HSPCF及其相应络合物反应行为的差别;讨论了胶束对络合反应速度的影响。     

吉非替尼的合成工艺改进

以3-羟基-4-甲氧基苯甲醛为原料,先与N-(3-氯丙基)吗啉缩合,后依次经过醛基转化为氰基、硝化、还原、与3-氯-4-氟苯胺环合等反应合成了抗肿瘤药物吉非替尼,总收率约50%。其结构经1H NMR,MS和元素分析表征。     

氯沙坦的合成工艺改进

以2-氰基-4′-溴甲基联苯和2-丁基-4-氯-5-甲酰基 咪唑为原料,依次经N-烷基化、羟基化和四唑化反应合成了氯沙坦,总收率73.9%,其结构经¹H NMR和MS（ESI）确证。     

2-氰基-3-取代氨基-3-(2-甲基苯基)丙烯酸乙酯的合成和杀菌活性

2-甲基苯甲酰氯与氰乙酸乙酯反应得到2-氰基-3-羟基-3-(2-甲基苯基)丙烯酸乙酯, 经氯化得到2-氰基-3-氯-3-(2-甲基苯基)丙烯酸乙酯, 再用三乙胺处理合成了11个2-氰基-3-取代氨基-3-(2-甲基苯基)丙烯酸乙酯类目标化合物. 生物活性研究表明这类新化合物具有良好的杀菌活性.     

离子液体[bmim]Cl/AlCl_3催化5-氰基吲哚酰化反应

5-氰基吲哚与4-氯丁酰氯之间的傅-克酰化反应使用路易斯酸之类的催化剂(如AlCl3、FeCl3),反应产物复杂,无法分离出期望的产物5-氰基-3-(4-氯丁酰基)吲哚。在离子液体[bmim]Cl/AlCl3中,进行5-氰基吲哚与4-氯丁酰氯间的傅-克酰化反应,则反应的主产物是5-氰基-3-(4-氯丁酰基)吲哚,产物结构通过质谱与核磁共振氢谱表征。考察了[bmim]Cl/AlCl3中AlCl3与[bmim]Cl间的摩尔比以及[bmim]Cl/AlCl3与5-氰基吲哚的摩尔比对该酰化反应的影响。结果表明,当n(AlCl3)∶n([bmim]Cl)=2.5∶1,n([bmim]Cl/AlCl3)∶n(5-氰基吲哚)=2∶1,室温下反应24 h,最大产率71.7%。     

螺环三代树形大分子化合物的合成

以对苯二甲醛单缩醛与季戊四醇反应得到了2,4,8,10-四氧杂-2,9-二(4-二氰基乙烯基苯基)螺[5.5]十一烷(1), 经水解, 再与丙二腈反应, 制备了中间体2,4,8,10-四氧杂-2-(4-二氰基乙烯基苯基)-9-(4-甲酰基苯基)螺[5.5]十一烷(3). 8-(4-氧代环己烷基)-1,4-二氧杂螺[4.5]癸烷经芳构化形成2,6,10-三-(4-氧代环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(4), 再与甲醛进行羟醛缩合, 制成了2,6,10-三-(4-羟基-3,3,5,5-四羟甲基环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(5), 将5与过量的3反应, 得到了目标树形大分子化合物2,6,10-三-{15-(3,11-二(-4-(3-((9-(4-二氰基乙烯基)苯基)2,4,8,10-四氧杂螺[5.5]十一烷基)))-7-羟基-二螺[5.1.5.3]十六烷基)}-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(6), 收率为18.1%. 产品结构经IR, 1H NMR, MS和元素分析进行了表征. 对影响反应的因素进行讨论.     

含磷拟除虫菊酯的研究III. 3-烷氧羰基-2, 2-二甲基环丙烷基 甲醛肟或甲基酮 肟和二烷氧基硫代磷酰氯的反应

本文研究了3-烷氧羰基-2,2-二甲基环丙烷基甲基酮肟或醛肟分别和二烷氧基硫代磷酰氯的反应,鉴定了它们的不同产物。结果表明,酮肟与磷酰氯缩合得硫代磷酸肟酯;醛肟与磷酰氯反应生成3-氰基环丙烷羧酸酯和相应的二烷基硫代磷酸,可能是经生成9再Beckmann裂解的机理。文中对上述结果进行了讨论。     

含磷拟除虫菊酯的研究III. 3-烷氧羰基-2, 2-二甲基环丙烷基 甲醛肟或甲基酮 肟和二烷氧基硫代磷酰氯的反应

本文研究了3-烷氧羰基-2,2-二甲基环丙烷基甲基酮肟或醛肟分别和二烷氧基硫代磷酰氯的反应,鉴定了它们的不同产物。结果表明,酮肟与磷酰氯缩合得硫代磷酸肟酯;醛肟与磷酰氯反应生成3-氰基环丙烷羧酸酯和相应的二烷基硫代磷酸,可能是经生成9再Beckmann裂解的机理。文中对上述结果进行了讨论。     

新方法合成4-氰基-1-茚酮

以邻氰基氯苄和丙二酸二乙酯为原料,经缩合、碱水解、脱羧和Friedel-Crafts酰化反应合成了4-氰基-1-茚酮,总收率32.1%,其结构经1H NMR和13C NMR确证。     

4-甲氧基-3-[3-(吗啉-4-基)丙氧基]苯甲腈的合成研究

以3-羟基-4-甲氧基苯甲醛为原料,在甲酸、甲酸钠、盐酸羟胺作用下,将醛基转化为氰基,在含有碳酸钾的DMF中,所得化合物与N-(3-氯丙基)吗啉反应得目标化合物,总收率为87.5%。产物结构由1HNMR表征。本方法具有操作简单、易于纯化、收率高等特点,为工业化生产提供实验基础。     

AAPBA@KCC-1的合成及其对血清中唾液酸和神经节苷脂的分析应用

将3-丙烯酰胺基苯硼酸(AAPBA)修饰在介孔二氧化硅KCC-1的表面,合成AAPBA@KCC-1材料,并通过扫描电子显微镜、透射电子显微镜、N_2吸附解吸附测试和X射线光电子能谱对其进行表征;将AAPBA@KCC-1材料作为分散固相萃取(dSPE)的吸附剂,对血清样品中的唾液酸和神经节苷脂(GLS)进行提取和富集;采用傅里叶变换离子回旋共振质谱法和超高效液相色谱-离子淌度-四极杆飞行时间质谱法分别对AAPBA@KCC-1材料吸附得到的唾液酸和神经节苷脂进行分析。结果表明,AAPBA@KCC-1材料能够有效吸附唾液酸和神经节苷脂,简化了样品前处理的操作,可以进一步应用于生物样品中唾液酸和神经节苷脂的研究。     

钨酸催化氧化环己烯合成己二酸

以钨酸/有机酸性添加剂为催化体系, 在无有机溶剂、相转移剂的情况下, 催化30%过氧化氢氧化环己烯合成己二酸. 当钨酸∶有机酸性添加剂∶环己烯∶过氧化氢＝1∶1∶40∶176(摩尔比, 钨酸用量为2.5 mmol)时, 使用有机酸性添加剂考察钨酸的催化性能, 结果表明以钨酸/间苯二酚催化氧化环己烯的催化效果最优, 反应8 h时己二酸分离产率达90.9%、纯度为～100%; 而不使用有机酸性添加剂时, 己二酸分离产率只有72.1%, 产品纯度为96.2%. 当使用磺酸水杨酸、草酸、水杨酸为有机酸性添加剂时, 随反应时间的增加, 己二酸分离产率均升高, 但反应6 h以后, 己二酸分离产率随时间的变化不明显. 当磺酸水杨酸用量为2.5 mmol时, 己二酸分离产率和纯度均较高. 钨酸-磺酸水杨酸催化体系重复使用五次后, 己二酸分离产率仍可达到80.5%.     

胶束电动毛细管色谱法测定板蓝根中苯甲酸、水杨酸和邻氨基苯甲酸

采用胶束电动毛细管色谱法对板蓝根中芳香酸类化合物苯甲酸、水杨酸和邻氨基苯甲酸进行了分离测定。电泳介质(pH 9.8)为20 mmol.L-1硼砂、30 mmol.L-1十二烷基硫酸钠、2 mmol.L-1β-环糊精和4%(体积分数)甲醇组成的混合溶液,以对-羟基苯甲酸为内标,分离电压为16 kV,检测波长为250 nm。在优化的试验条件下,苯甲酸、水杨酸和邻氨基苯甲酸的线性范围分别为40～240 mg.L-1,64～320 mg.L-1和40～400 mg.L-1,检出限(3S/N)依次为0.64,1.08,1.36 mg.L-1。应用此方法分析了板蓝根样品,测定回收率在93.3%～104.2%之间。     

Micellar electrokinetic chromatography of bilirubin, related compounds, and selected drugs with mixtures of binary bile salts

Micellar electrokinetic chromatography was used to study the behavior of quinine, propranolol, bilirubin, biliverdin dimethyl ester, and xanthobilirubin methyl ester in single and binary bile salt micelle systems comprised of glycocholic acid and glycodeoxycholic acid. Micelle systems studied had total bile salt concentrations in the range of 10-33 mM with molar ratios of 1:0, 2:1, 1:1, 1:2, and 0:1 glycocholic acid:glycodeoxycholic acid. A pH 8.5 phosphate-borate buffer system was used. For all analytes except bilirubin, the smallest migration factors were found in glycocholic acid solutions and the largest in glycodeoxycholic acid solutions. Intermediate migration factors were found for all compounds except bilirubin in the binary bile salt systems. Bilirubin behaved uniquely with its largest migration factors in the binary bile salt mixtures.     

氨基磺酸催化合成-萘乙酸甲酯

氨基磺酸能够代替硫酸作为酯化催化剂。在氨基磺酸存在下,由1-萘乙酸和甲醇酯化合成了高收率的1-萘乙酸甲酯。研究了反应的影响因素和催化剂的重复使用性能。当1-萘乙酸、甲醇和氨基磺酸的质量比为1:10:1,回流反应5h时,酯收率达97.5%。     

Studies on the extraction and determination of metal salts with isobutyl methyl ketone-XIV Extraction of gold

The isobutyl methyl ketone extraction of gold(III) from hydrochloric acid or various mixtures of hydrochloric and other mineral acids was studied as a function of the gold concentration and the acid concentration. Gold (initial concentration up to 5 x 10(-3)M) was quantitatively extracted (99%) from 3-5M hydrochloric acid. Addition of nitric acid in 1-5M concentration and sulphuric or perchloric acid in 1-3N concentration to the 1-5M hydrochloric acid solutions used had no effect.     

Direct TLC Resolution of (±)-Ketamine and (±)-Lisinopril by Use of (+)-Tartaric Acid or (−)-Mandelic Acid as Impregnating Reagents or Mobile Phase Additives. Isolation of the Enantiomers

Direct resolution of the enantiomers of the racemic drugs ketamine and lisinopril has been achieved by TLC. Enantiomerically pure tartaric acid and mandelic acid were used as chiral impregnating reagents and as mobile phase additives. When (?)-mandelic acid was used as chiral impregnating reagent use of ethyl acetate–methanol–water 3:1:1 (v/v) as mobile phase enabled successful resolution of the enantiomers of both compounds. For lisinopril, the mobile phase acetonitrile–methanol–water–dichloromethane 7:1:1:0.5 (v/v) was successful when (+)-tartaric acid was used as impregnating agent. When (+)-tartaric acid was used as mobile phase additive the mobile phase acetonitrile–methanol–(+)-tartaric acid (0.5% in water, pH 5)–glacial acetic acid 7:1:1.1:0.7 (v/v) enabled successful resolution of the enantiomers of lisinopril. The effects on resolution of temperature, pH, and the amount of chiral selector were also studied. The separated enantiomers were isolated and identified. Spots were detected with iodine vapour. LODs were 0.25 and 0.27 μg for each enantiomer of ketamine with (+)-tartaric acid and (?)-mandelic acid, respectively, whereas for lisinopril LODs were 0.14 and 0.16 μg for each enantiomer with (+)-tartaric acid (both conditions) and (?)-mandelic acid, respectively.     

MALDI-TOFMS测定高聚合度葡聚糖及不同基体在测定中的作用比较

应用基体辅助激光解吸电离飞行时间质谱(MALDI-TOFMS)直接对未经分级的高聚合度(n>100)葡聚糖样品进行了测定,检测到的葡聚糖最大分子量达18000以上.对2,5-二羟基苯甲酸(DHB)、1-羟基异喹啉(1-HIQ)及3,4-二羟基肉桂酸(咖啡酸,CA)3种一元基体以及DHB与1-HIQ,DHB与CA两种二元基体在测定中的作用进行了比较.结果表明,DHB基体测定的质量范围较大;DHB+1-HIQ和DHB+CA二元混合基体对样品的解吸电离效果及谱图重现性好;DHB+1-HIQ基体获得的谱图分辨率高.     

Comparison of two cryptand separator columns for the determination of trace chloride in semiconductor-grade nitric acid

Improved ion-chromatographic approaches for measuring trace chloride in nitric acid are presented. Two columns, the IonPac Cryptand A1 and a higher-capacity Cryptand prototype, were tested and compared. Also, the use of a Continuously Regenerated Anion Trap Column (CR-ATC) was evaluated for its ability to purify electrolytically generated eluent. Nitric acid (70%) was used as the test matrix and chloride was used as the test analyte; prior to injection, the nitric acid was diluted to 0.7% for the A1 column and to 2.8% for the prototype column. Chloride could be quantified in only 20 min on either column; detection limits computed for 70% HNO3 (at 95% confidence, alpha = beta = 2.5%) were 1.8 and 1.5 ppm for the A1 and prototype columns, respectively. Results also showed that the CR-ATC was necessary for obtaining acceptable acid blanks.     

微波辐射固体酸催化合成己二酸二正辛酯

采用微波辐射技术 ,以活性炭担载对甲苯磺酸为催化剂 ,由己二酸和正辛醇直接酯化合成己二酸二正辛酯。用正交试验研究了各反应因素对反应转化率的影响 ,确定其最佳反应条件为 :己二酸的用量 1mmol,正辛醇的用量 4mmol,催化剂用量为 0 .8g ,微波功率 6 0 0W ,辐射时间 45s ,转化率为 99.3 % ,催化剂且可重复使用。