2-甲氧基-3-溴-5-硝基苯基苄基醚的合成方法研究

研究了安莎霉素类天然产物reblastatin芳核片段2-甲氧基-3-溴-5-硝基苯基苄基醚的合成方法.该合成路线的关键步骤是苯甲醛中间体的Baeyer-Villiger反应,此反应易生成羧酸副产物.通过对反应试剂和操作的优化,以84%的高产率获得了预期产物酚.该路线以5步直线步骤和33%的总收率实现了2-甲氧基-3-溴-5-硝基苯基苄基醚的制备.     

高聚物型色谱柱分析1-苯基-2-硝基丙烯

建立了测定1-苯基-2-硝基丙烯及相关物质的高效液相色谱法,并利用该方法对1-苯基-2-硝基丙烯在乙腈溶液中的稳定性进行了探讨。选用以聚苯乙烯二乙烯基苯(PS-DVB)为基质的MKF-RP-HH高聚物型色谱柱(250mm×4.6 mm,6μm,ZH-1129-03),以乙腈(ACN)-水作为流动相,梯度洗脱(0~8 min,74%→92%ACN体积分数),流速为1.0 mL/min,在214和250 nm波长下进行检测。结果显示,硝基乙烷、苯甲醛和1-苯基-2-硝基丙烯3种物质可达很好的分离,其分离度均大于1.5;检出限(LOD)分别为0.031、0.006和0.011μg/mL;相对标准偏差(RSDs)在0.16%~0.66%之间。1-苯基-2-硝基丙烯乙腈溶液在光照条件下不稳定。此种检测方法简便快捷,结果准确可靠,可用于1-苯基-2-硝基丙烯的质量检测。     

3-(4-羟基苯基)-2-羟甲基-8-甲氧基1-,4-苯并二氧六环-8-醛的合成

以3-甲氧基-4-羟基苯甲醛和对羟基苯甲醛为起始原料,分别经过溴代和水解两步反应制得3-甲氧基-4,5-二羟基苯甲醛;经过诺文葛耳反应、酯化、还原三步反应制得对羟基苯基丙烯醇.3-甲氧基-4,5-二羟基苯甲醛和对羟基苯基丙烯醇以氧化银为氧化剂,通过自由基仿生氧化偶联反应合成了目标化合物3-(4-羟基苯基)-2-羟甲基-8-甲氧基-1,4-苯并二氧六环-6-醛,其总收率为11.2%.以氧化银为氧化剂的自由基仿生氧化偶联反应为反应的关键步骤.     

3-(4-羟基苯基)-2-羟甲基-8-甲氧基-1,4-苯并二氧六环-6-醛的合成

以3-甲氧基-4-羟基苯甲醛和对羟基苯甲醛为起始原料，分别经过溴代和水解两步反应制得3-甲氧基-4,5-二羟基苯甲醛；经过诺文葛耳反应、酯化、还原三步反应制得对羟基苯基丙烯醇.3-甲氧基-4，5-二羟基苯甲醛和对羟基苯基丙烯醇以氧化银为氧化剂，通过自由基仿生氧化偶联反应合成了目标化合物3-（4-羟基苯基）-2-羟甲基-8-甲氧基-1，4-苯并二氧六环-6-醛，其总收率为11．2％．以氧化银为氧化剂的自由基仿生氧化偶联反应为反应的关键步骤．     

5-(4-羧基苯基)-10,15,20-三(4-甲氧基苯基)卟啉的合成与表征

介绍了一种以吡咯、4-甲氧基苯甲醛和对羧基苯甲醛为原料,"一锅法"制备5-(4-羧基苯基)-10,15,20-三(4-甲氧基苯基)卟啉的简单方法,目标产物产率约为5.2%.对产物用紫外可见光谱、红外光谱、氢核磁共振谱进行了结构表征.     

氯化亚锡催化还原合成4-氨基苯基马来酰亚胺研究

本文研究了氯化亚锡催化还原4-硝基苯基马来酰亚胺并合成了一种新型的NPMI类化合物——N-（4-氨基苯基）马来酰亚胺,考察了温度、催化剂、中合剂、萃取剂、酸度和萃取次数等因素对反应的影响,确定了反应的优化条件。在反应温度60℃、n（氯化亚锡）：n（4-硝基苯基马来酰亚胺）=5：1、n（盐酸1：1）：n（4-硝基苯基马来酰亚胺）=20：1、无水碳酸钙作中合剂、乙酸乙酯作萃取剂、萃取次数6次的条件下,4-氨基苯基马来酰亚胺收率在50%左右。     

(R,R)-1,2-双[(2-甲氧基苯基)苯基膦]乙烷的合成

以苯基二氯化膦为基础原料,经与甲醇反应后发生阿布佐夫重排得到甲基苯基亚膦酸酯,然后与五氯化膦反应生成甲基苯基膦酰氯;甲基苯基膦酰氯与手性辅助试剂5反应,然后再与2-甲氧基苯基溴化镁反应生成具有单一构型的(S)-(2-甲氧基苯基)甲基苯基氧化膦.膦氧化物7经二异丙基氨基锂(LDA)锂化,再通过氯化铜偶联,最后与三氯硅烷和三丁胺反应以89.5%收率和98.3/1.7 dr值(两个非对映异构体的比值)得到目标产物(R,R)-1,2-双[(2-甲氧基苯基)苯基膦]乙烷.     

N-邻硝基苯基-N′-2,4-二硝基苯基氨基脲的阴离子识别

设计合成了2个新型含内氢键阴离子识别受体N-邻硝基苯基-N′-2,4-二硝基苯基氨基脲(1)和N-邻硝基苯基-N′-4-硝基苯基氨基脲(2).利用核磁、质谱和元素分析等手段对这2个受体进行表征,利用紫外-可见光谱、荧光光谱、核磁滴定和裸眼识别进行了这2个受体对Ac O-、F-、H2PO4-、Cl-、Br-、I-等6种阴离子识别性能的研究.结果表明,这2个受体对Ac O-比其他阴离子具有较好的识别能力和选择性.受体1较受体2具有更强识别能力和选择性.     

2,2-二(3-硝基-4-羟基苯基)六氟丙烷的合成

2,2-二(3-硝基-4-羟基苯基)六氟丙烷作为合成2,2-二(3-氨基-4-羟基苯基)六氟丙烷的中间体,其合成对于2,2-二(3-氨基-4-羟基苯基)六氟丙烷的合成至关重要。目前,关于2,2-二(3-硝基-4-羟基苯基)六氟丙烷的合成,共有两种专利方法:美国专利和日本专利。本文将对这两个专利的反应条件进行讨论、比较和分析,分别优化出两个专利的最适宜的反应条件,从而优选出最佳的合成路线。结果表明:日本专利的2,2-二(3-硝基-4-羟基苯基)六氟丙烷的合成方法步骤简单,产率高,适合于工业化生产。     

5-(2-甲氧基羰基-E-乙烯基)-7-甲氧基-2-(4-苄氧基苯基)苯并〔b〕呋喃的合成

目的:以对-羟基苯乙酮为原料,经烷基化、Vislsmeier反应等,合成5-(2-甲氧基羰基-E-乙烯基)-7-甲氧基-2-(4-苄氧基苯基)苯并〔b〕呋喃。方法:查阅、分析、归纳相关文献设计出5-(2-甲氧基羰基-E-乙烯基)-7-甲氧基-2-(4-苄氧基苯基)苯并〔b〕呋喃的合成路线,运用化学合成法合成该目标产物,并检测其纯度。结果:通过实验研究,合成了5-(2-甲氧基羰基-E-乙烯基)-7-甲氧基-2-(4-苄氧基苯基)苯并〔b〕呋喃。结论:5-(2-甲氧基羰基-E-乙烯基)-7-甲氧基-2-(4-苄氧基苯基)苯并〔b〕呋喃的熔点170~171℃,收率25.2%,纯度99.08%。     

磷桥联双金属配合物结构优化的量子化学方法研究

采用Hartree-Fock(HF)及密度泛函理论（Density Functional Theory,DFT）方法，在LANL2DZ和CEP-31G基组水平上，对配合物CpW(CO)₂(μ-CO)(μ-PPh₂)Fe(CO)₃(1)和CpW(CO)₃(μ-PPh₂)Fe(CO)₄(2)的结构进行了优化，并将采用不同方法和基组的优化结果与X射线衍射实验数据对照。结果表明，用量子化学方法优化含重金属原子的较大配合物体系的结构是方便可行的，而且DFT方法在此类计算中有更高的准确度。为日后进一步深入开展含有过渡金属原子的双金属配合物的理论研究提供了可靠的计算依据。     

Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H₂NR)₂ and M(Por)(HNR′₂)₂, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF₄ as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp₂ Fe^+/0 (Cp₂Fe=ferrocene) for Ru(TPP)(H₂NBu-t)₂, Ru(4-Cl-TPP) (H₂NBu-t)₂ and Ru(3,5-Cl-TPP)(H₂NBu-t)₂ respectively. Supported by the foundation of the Chinese Education Commission Li Zaoying: born in 1949, Associate Professor     

Electrochemical behavior of novel bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins

Bis (aliphatic amine) ruthenium (II) and osmium (II) porphyrins, M (Por)-(H₂NR)₂ and M(Por)(HNR′₂)₂, [M=Ru and Os; Por=meso-tetrakis (p-tolyl) porphyrinato (TTP), meso-tetrakis (4-chlorophenyl) porphyrinato (4-Cl-TPP), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP) and meso—tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R′=methyl and ethyl] were synthesized by us. The electrochemical behavior of these complexes in 1, 2-dichloroethane with TBABF₄ as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis (aliphatic amine) ruthenium (II) porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium (II) analogues is shown two oxidation couples III and V, an additional small wave IV. The redox potentials of these complexes are markedly dependent on the nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at −0.34, −0.23 and −0.15 V vs Cp₂ Fe^+/0 (Cp₂Fe=ferrocene) for Ru(TPP)(H₂NBu-t)₂, Ru(4-Cl-TPP) (H₂NBu-t)₂ and Ru(3,5-Cl-TPP)(H₂NBu-t)₂ respectively. Supported by the foundation of the Chinese Education Commission Li Zaoying: born in 1949, Associate Professor     

非晶态合金(Fe_(100-x)M_x)_(83)B_(17)和Zr_(100-x)M_x的杨氏模量

用超声波脉冲透射技术获得了三元非晶态合金(Fe_(100-x)M_x)_(83)B_(17)和二元非晶态合金Zr_(100-x)M_x的声速,并确定了它们的杨氏模量。对于前者合金元素M指Cr,Mo,W,Zr和Co;对于后者指Fe,Ni和Co。文中讨论了声速与组分的原子百分数含量x之间的关系,并讨论了近程有序,合金元素密度以及不同尺寸原子之间的随机堆砌引起的致密化等对声速的影响。     

Electroluminescent property of tetrakis(phenyl)porphyrin carbonyl ruthenium(Ⅱ)

Luminescent tetrakis(phenyl)porphyrin carbonyl ruthenium (Ⅱ) (RuTPPCO) complex was employed as a doped emitting material to fabricate red organic electroluminescent (EL) devices. The EL device structure was [ITO/copper phthalocyanine (Cu-Pc) (15.0 nm)/N,N′-di(α-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4, 4′-diamine (NPB)(60.0 nm)/tris(8-hydroxyquinolinato)aluminum (Alq3):RuTPPCO (50.0 nm)/LiF (1.0 nm)/Al (200.0 nm)]. The codeposited films of Alq3:RuTPPCO were utilized as the emitting layer to construct EL devices. Experimental results showed that energy transfer from Alq3 to RuTPPCO occurred in the codeposited films. The EL property of the codeposited Alq3:RuTPPCO films with different RuTPPCO concentrations was described. For the EL device with the RuTPPCO concentration of 15% by weight, deep red electroluminescence at 656 nm with the maximum EL efficiency of 0.32 cd/A was achieved.     

Synthesis and spectroscopy of nitridoruthenium (VI) and osmium (VI) porphyrins

Reaction of Ru (4-Cl-TPP) (CO) (MeOH) [4-Cl-TPP = meso-kis (4-chlorophenyl) porphyrinato dianion] with 3-chloroperoxybenzoic acid (m-CPBA) followed by treatment of the mixture with an aqueous ammonia solution afforded the first nitrido ruthenium porphyrin Ru(4-Cl-TPP) (N) (OH). Three new nitrido osmium (VI) porphyrins, Os (Por) (N) (OH) (Por=TPP, TTP, and 4-Cl-TPP), were synthesized from oxidation of Os(Por)(NH₃)₂ withm-CPBA. All these new complexes were characterized by¹H NMR, IR, UV/Visible spectra and elemental analyses. Both nitrido ruthenium (VI) and osmium (VI) porphyrins are diamagnetic. Their pyrrole proton resonances appear at slightly lower fields than those of the corresponding dioxo Ru(VI) and Os(VI) porphyrins. The {ie89-1}, or {ie89-2}, region is obscured by the strong “oxidation state marker” band. Li Zaoying: born in July 1949, associate professor. Curent research interest is in the study on synthesis and properties of macrocyclic polyamine and complexes     

SU(N)与SO(2N)代大统一模型分析

本文应用SU(N)×S与SO(2N)×S作为大统一规范群,对代大统一模型的各种方案进行了全面分析。我们的结论是:SU(7)×S,SU(8)×S,SO(14)×S和SO(16)×S是比较好的代大统一规范群。本文给出了SO(14)×S与SO(16)×S两个代大统一模型。它们容纳了四代通常费米子,并保持SU(3)c渐近自由性质。模趔保留了SO(10)模型中得到的全部好的结果,克服了标准大统一模型中“代“的困难。     

Na_(3.3)Zr_(1.65-X)Ti_XSi_(1.9)P_(1.1)O_(11.5)系统的相组成及性能

通过高温（１１７３—１４７３Ｋ）固相反应．制备了钠快离子导体ＮＡ３．３Ｚｒ１．６５－ＸＴｉＸＳｉ１．９ Ｐ１．１Ｏ１１．５系统中Ｘ＝０－１．６５的一系列合成物，研究了该系统的相变情况，探明了在ｘ＝０．５－０．９ 的组成范围内可制得ＮＡＳＩＣＯＮ单相．其中电导性最好的是Ｘ＝０．６的合成物．在６２３ｋ时它的电导 率为１８．９Ｓ·ｍ－１，在４７３—６７３Ｋ温区里其电导激活能为４１．７ＫＪ／ｍｏｌｅ．     

A Novel Degradation Pathway of Zn（dmid） （ phen）2 in Pyridine

The light-oxidation degradation processes of Zn(dmid)(phen)2(dmid = 4, 5-dimercapto-1,3-dithiole-2 one, phen = 1,10-phenanthroaline) in pyridine solvent has been monitored, h has been found under the light, dmid^2- of Zn(dmid)(phen)2 in pyridine solution could generate NCS^- and NCS^-replaces dmid^2- to form Zn(NCS)2 (phen)2 simultaneously. The crystal structure of Zn(NCS)2 (phen)2 has been determined. In the crystal of Zn(NCS)2 (phen)2. two NCS^- ligands are arranged in syn-configuration, and there is strong π-π interaction between the two adjacent parallel phen.     

关于内(q)群(非ρ-群)

本文利用广幂零群对每个次正规子群为拟正规的群以及每个次正规子群为S-拟正规的群给出了一个统一的刻划,由此得到内(q)群与内(s-q)叶群的分类.