合成1,2-环十二二酮的新方法

以十二烷二酸（１）为原料,与甲醇酯化生成十二烷二酸二甲酯（２）,收率为８６５％。化合物２经偶联 缩合得１,２ 二三甲基硅氧基环十二烯（３）,收率为６３１％。利用溴氧化化合物３得到１,２ 环十二二酮（４）淡黄色晶体,收率７９％,全过程收率达４３.１％,是合成１,２ 二酮的新方法。目标化合物结构经红外光谱、核磁共振氢谱和碳谱表征确认。     

具有1,2-二苯基乙醇结构化合物的异常消除反应研究

报道了4个具有1,2-二苯基乙醇结构的化合物在酸性条件下发生消除反应, 得到未遵循Saytzeff规则的烯烃; 而在SOCl2/DMF条件下, 先氯代再消除则可获得一对双键位置异构的烯烃异构体. 通过计算机模拟, 采用Gaussian 98软件, B3LYP/6-31G方法对两种异构体进行了能量优化, 计算了它们的能量, 推测这类具有1, 2-二苯基乙醇结构化合物在酸性条件下的异常消除反应为动力学主导产物的反应.     

5′-硝基-水杨基荧光酮与头孢哌酮的显色反应

采用分光光度法,以5′-硝基-水杨基荧光酮(5′-NSAF)为显色剂,研究了5′-NSAF与头孢哌酮(CPZ)的络合物的可见光谱性质及反应条件。实验结果表明:头孢哌酮在6.68~133.6μg/mL范围内遵循比尔定律,回归方程为:A=0.0031ρ+0.023(ρ:μg/mL),检出限6.27μg/mL,表观摩尔吸光系数1.89×104L.mol-1.cm-1,相关系数为r=0.9970,并探讨了其反应机理。方法已用于尿样及生物样品中头孢哌酮含量的测定。     

化学修饰的大孔吸附树脂对1,2-苯并异噻唑-3-酮的吸附研究

选用在有机废水处理中已经得到广泛使用的商业化树脂Amberlite XAD-4作参照,通过等温吸附实验和吸附动力学实验研究了单宁酸和邻羧基苯甲酰基修饰的吸附树脂(分别命名为FZH-11和FZH5)对1,2-苯并异噻唑-3-酮的吸附性能。结果表明,修饰后的树脂FZH-11和FZH5对1,2-苯并异噻唑-3-酮具有较高的吸附容量,吸附过程存在化学吸附作用。1,2-苯并异噻唑-3-酮在FZH-11和FZH5树脂上的吸附过程符合准一级动力学方程,颗粒内扩散是吸附过程的主要速度控制步骤。FZH-11和FZH5树脂经酸液脱附可重复利用,废水在得到有效治理的同时实现了1,2-苯并异噻唑-3-酮的资源化回收利用。     

1,2-联烯基酮的合成与反应

1,2-联烯基酮可以通过2-丙炔基酮异构化反应,相应有机金属试剂中间体与酯、酰氯或酰胺的反应,[2,3]或[3,3]迁移反应,Wittig反应,消除反应,2,3-联烯醇氧化等方法合成。由于联烯酮上含有吸电子基团羰基,它可发生亲核加成、环加成、环化反应。     

氧气氧化2,6-二-(三甲基硅基)吡喃为6-三甲基硅基-α-吡喃酮

开发出一种合成6-三甲基硅基α-吡喃酮的有效方法.在无溶剂无任何催化剂的氧气气氛中,室温条件下温和地将2,6-二-(三甲基硅基)吡喃通过氧化反应转化成6-三甲基硅基α-吡喃酮,并且给出了该反应可能的机理.     

3-炔基咪唑并[1,2-b]哒嗪的简便合成

以咪唑并[1,2-b]哒嗪为原料,与N-碘代丁二酰亚胺在三氟乙酸/二氯甲烷中于室温进行碘代反应制得3-碘咪唑并[1,2-b]哒嗪(3);3与三甲基硅基乙炔在Pd(OAc)_2催化下经Sonogashira偶联反应制得3-三甲基硅基乙炔基咪唑并[1,2-b]哒嗪(4);4在碳酸钾作用下脱除三甲基硅基合成了3-炔基咪唑并[1,2-b]哒嗪,总收率61.2%,其结构经~1H NMR和HR-MS确证。     

α-单取代-1,2-环十二二酮单肟的合成及晶体结构

通过α-单取代环十二酮与亚硝酰氯反应合成了一系列α-单取代-1,2-环十二二酮单肟,它们的结构经1H NMR,13C NMR,ESI-MS和元素分析确证.X射线衍射和量子力学计算结果表明,α-单取代环十二酮与亚硝酰氯反应生成α-单取代-1,2-环十二二酮单肟时,生成产物具有[4233]-3-酮和[3333]-2-酮两种...     

5-炔基噁唑啉-2-酮的合成

以廉价易得的取代酸为原料,经取代、硝基还原、氨基磺酰化、炔基格氏试剂加成和羰基化环化反应合成了13个5-炔基噁唑啉-2-酮类化合物,收率为10.6%~71.8%。产物结构经¹H NMR和¹³C NMR确证。      

钌1,2-萘醌-1-肟配合物对aldol C—C成键反应的催化作用

在钌1,2-萘醌-1-肟(1-nqo)配合物cis,cis-[Ru(1-nqo)₂(CO)(NCMe)] (1)或trans,trans-[Ru(1-nqo)₂(PBu₃)₂] (2)的作用下, 氰基乙酸乙酯与取代苯甲醛发生aldol C—C成键反应. 根据GC-MS检测及HPLC分离结果, 对二苯甲醛的二个醛基可分别或同时与氰基乙酸乙酯发生aldol反应. ¹H NMR表征结果证明, 二种产物的双键构型均为反式. 其它取代苯甲醛的反应均给出单一反式aldol产物, 这表明该催化反应具有立体选择性. 配合物1的催化活性稍差, 产率不超过60%, 而配合物2的催化活性要高于1, 最高产率达99%.     

Cu2O/1-(2-methylhydrazine-1-carbonyl)-isoquinoline 2-oxide catalyzed C-N cross-coupling reaction in aqueous media

An experimentally simple, efficient, and inexpensive catalyst system was developed for the N-arylation of imidazole, indole, pyrrole, alkyl alcohol amines, and alkyl amines with aryl iodides and bromides. The reaction proceeds in water-ethanol media at 120 °C for 12 h with Cu₂O as the catalyst, 1-(2-methylhydrazine-1-carbonyl)-isoquinoline 2-oxide (L2) as the ligand, NaOH as the base to generate a wide range of N-arylated products in moderate to excellent yields. Aqueous medium, ease of operation, and broad substrate scope give the process a benign environmental profile.     

A novel method for the 1,2-carbonyl transposition of pleuromutilins

A new and efficient 1,2-carbonyl transposition procedure for the formation of 2-keto pleuromutilin compounds is described. The synthetic sequence is performed in four steps and 26% overall yield.     

N-(2-吡咯甲酰基)氨基酸甲酯的合成

在室温条件下,氨基酸甲酯和2-三氯乙酰基吡咯经酰基化反应,以80.3%～95.6%的产率合成了系列N-(2-吡咯甲酰基)氨基酸甲酯,通过1H NMR,IR,MS和元素分析对其结构进行了表征.     

Synthesis and Crystal Structure of 3-（1-Ethyl-1H-indole-3-carbonyl）aminopropionic Acid

3-(1-Ethyl-1H-indole-3-carbonyl)aminopropionic acid has been synthesized by alkylation of 3-(1H-indole-3-carbonyl)aminopropionic acid methyl ester with bromoethane,follo-wed by saponifying and acidating,in 89.0% yield.Its crystal structure was gotten and determined by X-ray diffraction method.The crystal is of orthorhombic,space group P212121 with a = 8.9490(12),b = 11.1010(15),c = 13.0475(18) ,V = 1296.2(3) 3,Z = 4,Dc = 1.334 g/cm3,λ = 0.71073 ,μ(MoKα) = 0.095 mm-1,Mr = 260.29 and F(000) = 552.The structure was refined to R = 0.0306 and wR = 0.1445 for 2612 observed reflections with I 2σ(I).In the crystal structure,molecules are linked to each other through hydrogen bonds of N(2)-H(2)···O(1) and O(3)-H(3)···O(1),generating a three-dimensional network.     

Multicatalytic synthesis of 1,2-dihydroisoquinolin-1-ylphosphonates via a tandem four-component reaction

A tandem four-component reaction of 2-bromobenzaldehyde, alkyne, amine, and diethyl phosphite catalyzed by the combination of palladium and copper salts provides a facile and efficient route to 1,2-dihydroisoquinolin-1-ylphosphonate. A cascade Sonogashira-intramolecular cyclization-nucleophilic addition may be involved in the reaction process.     

Simultaneous liquid chromatography-fluorescence analysis of type A and type B trichothecenes as fluorescent derivatives via reaction with coumarin-3-carbonyl chloride

A method for the simultaneous LC-fluorescence detection (FLD) determination of eight trichothecenes A and B by pre-column derivatization with coumarin-3-carbonyl chloride, a highly fluorescent fluorophore, has been developed. The reaction conditions (temperature, reaction time, reactant ratios) were optimized to give a reproducible quantitative conversion. All derivatives were characterized by LC-MS. The chromatographic parameters were optimized (column, eluent) to give a very good separation of three type A (diacetoxyscirpenol, T-2 toxin, HT-2 toxin) and five type B trichothecenes [deoxynivalenol (DON), nivalenol, fusarenon-X, 3-acetyldeoxynivalenol, 15-acetyldeoxynivalenol]. The best conditions were obtained on a narrow-bore C18 column with a water-methanol gradient. The detection limits (S/N = 3:1) in grain samples, with an injected volume of 5 microl, were 0.2-1 ng/g for all trichothecenes. These values are more than one order of magnitude lower than those of other LC-FLD and LC-MS methods and are similar to those obtained by GC-MS. The calibration curves were linear between 100 and 2500 ng/g. The method was successfully applied to the analysis of a certified wheat reference material, after solvent extraction and clean-up on a Mycosep column, obtaining a good recovery (89% for DON) and a high accuracy (z-score value: 0.67).     

Synthesis of chiral N-protected 1,2-dihydro-quinoline-2-carbonitrile and 1,2-dihydro-isoquinoline-1-carbonitrile via an asymmetric Reissert reaction

Addition of cyanide ion to chiral N-acyl-quinolinium and N-acyl-isoquinolinium salts led selectively to 1,2-addition products. Removal of the chiral auxiliary affords the title compounds in pure enantiomeric form.     

1，2－联烯亚砚和1，2－联烯砜的反应

1，2－联烯亚砜和1，2－联烯砜是重要的含硫联烯化合物，综述了1，2－联烯 亚砜和1，2－联烯砜的亲核加成、亲电加成、Diels-Alder反应、1，3－偶极加成 、[2+2]环加成等反应以及在天然产物中的应用。     

Determination of type A trichothecenes by high-performance liquid chromatography with coumarin-3-carbonyl chloride derivatisation and fluorescence detection

A method for the analysis of type A trichothecenes T-2 toxin, HT-2 toxin, neosolaniol and diacetoxyscirpenol by high-performance liquid chromatography with fluorescence detection using coumarin-3-carbonyl chloride has been developed. Different parameters concerning the analytical procedure such as stability of both the reagent and derivatised analytes, time and temperature of the derivatisation reaction, were studied and optimised. Three different clean-up procedures (solid-phase extraction with silica gel or C-18 cartridges, and liquid–liquid partition between toluene and dihydrogen phosphate buffer) were tested in order to remove the excess reagent peaks. The last procedure gave the best results when the buffer pH was 3–5.5, and is therefore recommended. Separations were performed on a stainless steel LiChrospher 100 C-18 reversed-phase column with pre-column of the same phase. The mobile phase was acetonitrile/water (65:35, v/v) containing 0.75% acetic acid at a flow-rate of 1.0 ml/min. The proposed method provides good separation between the four trichothecenes and good reproducibility (RSD of calibration standards <5%). The limits of detection of the studied trichothecenes at a signal-to-noise ratio of 3:1, with an injection volume of 20 μl were 10 ng/g sample for T-2 toxin and about 15 ng/g sample for the remaining mycotoxins. The calibration curve was linear between 10 and 2000 ng for the four trichothecenes assayed. The method was applied to the analysis of these mycotoxins in fungal cultures (corn and rice) of Fusarium sporotrichioides, and is also perfectly suitable for the quantification of type A trichothecenes in contaminated cereals.     

Synthesis and Crystal Structure of Methyl 3-（5- Bromo-1-ethyl-1H-indole-3-carbonyl）aminopropionate

Methyl 3-(5-bromo-1-ethyl-1H-indole-3-carbonyl)aminopropionate has been syn-thesized by the acylation of 5-bromo-3-trichloroacetylindole with β-alanine methyl ester,followed by alkylation with ethyl iodide,in 82.6% yield.Its crystal structure was gotten and determined by X-ray diffraction method.The crystal is of monoclinic,space group P2 1 /c with a=11.7927(8),b=14.9342(8),c=9.0060(5),β=101.558(6)°,V=1553.93(16)3,Z=4,D c=1.510 g/cm 3,λ=0.71073,μ(MoKα)=2.656 mm-1,M r=353.22 and F(000)=720.The structure was refined to R=0.0401 and wR=0.0825 for 1704 observed reflections with I > 2σ(I).In the crystal structure,intermolecular N(2)-H(2)···O(1) hydrogen bond and weak intermolecular bonds (C(1)-H(1) O(1) and C(10)-H(10B) O(2)) are formed,and π-π stacking also exists.