Synthesis,Redox Properties,and Electronic Spectra of Sterically Crowded Triarylphosphines Conjugated with Electron Acceptors

Abstract

Synthesis, redox properties, and electronic spectra of the sterically crowded triarylphosphines conjugated with π-electron systems, especially electron acceptors such as carbonyl group, are briefly reviewed. The sterically crowded triarylphosphines conjugated with various π-electron systems were synthesized from the common synthetic intermediate, (bromoaryl)phosphine, by conventional manner. The sterically crowded triarylphosphines conjugated with the electron acceptors exhibit visible absorption and fluorescence with large Stokes shift. Large solvent effect, redshift in polar solvent, and good correlation with the difference of the oxidation potential of the phosphine moiety and the reduction potential of the acceptor moiety suggest polar excited state resulting from HOMO-LUMO transition.     

Synthesis and Crystal Structure of 2,5—Bis（morpholino）—3,4—bis（p—chlorophenyl）thiophene

1 INTRODUCTION -Thiocarbonylthioformamide synthesized in 1980[1, 2] is a class of stable and almost unexplored compounds[3]. We have reported the reaction of - thiocarbonylthioformamides in our previous paper[4]. Here, we will report a novel synthesis of 2 by the reaction of 1 and trimethyl phosphite in refluxing xylene. In order to determine the structure of 2, X- ray crystallographic study was carried out. 2 EXPERIMENTAL 2. 1 Preparation of the title compound Trimethyl phosph…     

2,6-双(对羟基苯基偶氮)-9,10-蒽醌的合成

以2,6-二氨基蒽醌为原料,经硝酸钠与盐酸双重氮化制得2,6-二氨基蒽醌双重氮盐(2);2与苯酚偶合合成了未见文献报道的双偶氮类化合物--2,6-双(对羟基苯基偶氮)-9,10-蒽醌(3),其结构经1H NMR,IR,MS和元素分析表征.最佳的偶合反应条件为: 2 2.0 mmol,n(2) ∶ n(苯酚)＝1.0 ∶ 2.5,在pH=9的条件下,于0 ℃～5 ℃反应4 h,3的收率60%.     

2,6-二(5-烷基水杨基)-4-烷基苯酚的合成

以自制的正构长链烷基酚为原料与多聚甲醛在碱性催化剂下进行羟甲基化反应,生成2,6-二羟甲基-4-烷基苯酚,再与另两分子烷基酚在固体超强酸催化下进行缩合反应生成2,6-二(5-烷基水杨基)-4-烷基苯酚,用核磁共振氢谱和碳谱、红外光谱和元素分析对产物进行了结构鉴定,探讨了催化剂、反应物料配比、反应时间等条件对产物产率的影响.另外根据上述反应路线,以工业品壬基酚和多聚甲醛为原料,经羟甲基化反应、缩合反应合成了2,6-二(5-壬基水杨基)-4-壬基苯酚.上述两种结果表明,选用SO24-/SnO2固体超强酸作催化剂,2,6-二羟甲基-4-烷基苯酚和烷基酚的配比为1:2,140℃反应2h,产率达到95%.     

An Efficient Synthesis of Highly Optically Active 4-Substituted-2（5H）-furanones from Chiral 3-Bromo-2（5H）-furanone

Highly optically active 4-substituted-2(5H)-furanones 6a-6j were obtained in good yields with de≥98% by the tandem Michael addition/elimination reaction of chiral 3-bromo-2(SH)-furanone (4a), which was conveniently prepared starting from 2-furaldehyde under mild conditions. The products were identified on the basis of their satisfactory elemental analysis and spectroscopic data of IR, UV, ^1H NMR, ^13C NMR and mass spectra. The stereochemistry and absolute configuration of this type of compounds were established by the X-ray crystallographic study. The reaction provided a short and efficient synthesis of the interesting highly optically active 4-subsdtuted-2(5H)-furanones containing an active pyrimidine and a purine base group.     

基于2,6-二(4-羧基苯亚甲基)环己酮的金属-有机框架化合物的合成与表征

以2,6-二(4-羧基苯亚甲基)环己酮(H2L)为配体得到一例锰金属-有机框架化合物[MnL]n,并运用红外、热重、循环伏安、固体紫外、X射线光电子能谱和X射线单晶衍射对其进行表征.单晶衍射分析表明该配合物属于三斜晶系,空间群P(1),不对称单元由Mn(Ⅱ)离子和一个L2-配体组成.配体两端的羧基均为单齿配位,配体中间...     

2-溴-4,4'-二硝基-3'-二甲基锍-2'-联苯酚内盐的合成、结构及性质的研究

在胺存在下,3,7-二硝基二苯并溴五环硫酸氢盐与二甲基亚砜反应生成2-溴-4,4'-二硝基-3'-二甲基锍-2'-联苯酚内盐(3).3的X射线晶体结构分析数据表明其分子具有内盐结构但酚氧负离子的负电荷是部分离域的,分子内两苯环所成的两面角为117.3°.3在熔解时发生重排及热分解分别生成2-溴-2'-甲氧基-3'-甲硫基-4,4'-二硝基联苯(6)及3,7-二硝基-4-甲硫基-二苯并呋喃(7).3与盐酸反应生成相应的锍盐(8).     

Synthesis and Crystal Structure of 2,3-Bis(dinitrofluoromethyl)-1,4-dioxane

For the first time the dinitromethyl group was modified to dinitrofluoromethyl group in the series of aliphatic polynitro compounds in the case of the reaction of 1,1,4,4-tetranitro-2,3-butanediol diacetate with ammonium fluoroxysulfate in the presence of sodium bicarbonate and ethylene glycol. Previously unknown 2,3-bis(dinitrofluoromethyl)-1,4-dioxane was synthesized. Its structure was determined by X-ray diffraction analysis.     

Synthesis and Crystal Structure of 2,6-Bis（benzimidazo（1,2-c）- quinazolin-6-yl）pyridine Tetrahydrate

The title compound, 2,6-bis（benzimidazo（1,2-c）quinazolin-6-yl）pyridine tetrahydrate, was synthesized by simple condensation of 2-（2-sminophenyl） benzimidazole with pyfidine- 2,6-dicarboxylic acid and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 22.226（8）, b = 16.730（7）, c = 16.820（5）A, β = 115.796（13）°, V = 5631（4）A^3, C33H27NTO4, Mr = 585.62, Z = 8, Dc = 1.381 g/cm^3, λ（MoKα） = 0.71073 A, F（000） = 2448 and μ = 0.09 mm^-1. The structure was refined to the final R = 0.0730 and wR = 0.1573 for 6346 independent reflections （Rint = 0.0801） and 3384 observed reflections （I 〉 2σ（I））. In the crystal, the molecules are linked through intermolecular O-H…O and O-H…N hydrogen bonds. Intermolecular π-π interactions （with distances of about 3.45 A） are pronounced in the crystal structure.     

2,6-双(3-甲基-1-苯基-5-吡唑啉酮-4-基)吡啶二酮的合成

首次通过一步反应合成了2,6-双（3-甲基-1-苯基-5-吡唑啉酮-4-基）吡啶二酮,其结构经1^H NMR,IR和元素分析表征。     

Synthesis and Crystal Structure of Calix[4]arene Bearing a 1,8-Bis（propoxy）anthracene-9,10-dione

The title complex （C50H44C14O8） was synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/n with a = 19.7768（4）, b =10.2085（2）, c = 21.2721（4）A,β= 97.153（1）°, V = 4261.23（14）A^3, Z = 4, Mr = 914.65, F（000） = 1904, Dc = 1.426 g/cm^3,μ = 0.336, the final R = 0.0550 and wR = 0.1647. The compound was structurally characterized by IR and ^1H NMR. The molecules are stacked through C-H...π interactions and intermolecular C-H...O hydrogen bonds.     

Synthesis and Crystal Structure of 5-Amino-7-benzylseleno-8-cyano-3-ethoxycarbonyl-4-(2-furyl)-1,2-dimethyl-1,4-dihydro-1,6-naphthyridine

5-Amino-7-benzylseleno-8-cyano-3-ethoxycarbonyl-4-(2-furyl)-1,2-dimethyl-1,4-dihydro-1,6-naphthyridine was obtained by N-alkylation. X-ray crystallography showed the presence of two symmetrically conformers in the crystal.     

Synthesis and Characterization of 2,6-Bis(imino)phenoxy Cobalt Complexes

ＩｎｔｒｏｄｕｃｔｉｏｎＲｅｃｅｎｔｒｅｓｅａｒｃｈｅｆｆｏｒｔｓｈａｖｅｂｅｅｎｄｅｖｏｔｅｄｔｏｔｈｅｓｔｕｄｙｏｆｌａｔｅｔｒａｎｓｉｔｉｏｎｍｅｔａｌｃｏｍｐｌｅｘｅｓａｓｍｏｄｅｌｓｙｓｔｅｍｓｆｏｒｔｈｅｐｏｌｙｍｅｒｉｚａｔｉｏｎｏｒｏｌｉｇｏｍｅｒｉｚａｔｉｏｎｏｆｅｔｈｙｌｅｎｅ .1 3ＴｈｅｍｏｓｔｎｏｔａｂｌｅａｃｈｉｅｖｅｍｅｎｔｓｈａｖｅｂｅｅｎｄｏｎｅｂｙＢｒｏｏｋｈａｒｔ,4 Ｂｅｎｎｅｔｔ,5ａｎｄＧｉｂｓｏｎｇｒｏｕｐｓ .6,7Ｔｈｅｙｉｎｄｅ ｐｅｎｄｅｎｔｌｙｒｅｐｏｒ…     

Synthesis of a Hexameric Magnesium 4-pyridyl Complex with Cyclohexane-like Ring Structure via Reductive C-N Activation

The reaction of [{(^Arnacnac)Mg}₂] (^Arnacnac = HC{MeC(NAr)}₂, Ar = 2,6-diisopropylphenyl, Dip, or 2,6-diethylphenyl, Dep) with 4-dimethylaminopyridine (DMAP) at elevated temperatures afforded the hexameric magnesium 4-pyridyl complex [{(^Arnacnac)Mg(4-C₅H₄N)}₆] via reductive cleavage of the DMAP C-N bond. The title compound contains a large s-block organometallic cyclohexane-like ring structure comprising tetrahedral (^Arnacnac)Mg nodes and linked by linear 4-pyridyl bridging ligands, and the structure is compared with other ring systems. [(^Dipnacnac)Mg(DMAP)(NMe₂)] was structurally characterised as a by-product.     

9,9-二[4-(4-羧基苯氧基)苯基]呫吨的合成

在碘化亚铜、四丁基溴化铵和磷酸钾存在下,9,9-二(4-羟基苯基)呫吨(1)和4-甲基碘苯(2)于N,N-二甲基甲酰胺溶剂中发生Ullmann偶联反应,加热回流反应24 h,以95%的产率合成了中间体--9,9-二[4-(4-甲基苯氧基)苯基]呫吨(3),继而加入催化量的N-溴代丁二酰亚胺并在光照条件下,将中间体3氧化得到一种新型芳香族二羧酸--9,9-二[4-(4-羧基苯氧基)苯基]呫吨(4),其产率为84%,二步反应总收率为79.8%。 目标化合物4经1H NMR、13C NMR、IR和元素分析测试技术确定了其结构。 该法具有原料易得,操作简单,反应条件温和,收率高等优点。     

4-溴-5-硝基邻苯二甲腈的合成及晶体结构

以邻苯二甲酸酐为原料,经溴化、脱水、亚胺化、硝化、酰胺化、脱水6步反应合成了一种易调变的酞菁前驱体——4-溴-5-硝基邻苯二甲腈,并测定了其晶体结构。     

Synthesis and Crystal Structure of 2,6-Bis（2-pyridinylmethyl）-3,5-bis（2-hydroxyl-5-chlorophenyl）pyrazine

The title compound,2,6-bis(2-pyridinylmethyl)-3,5-bis(2-hydroxyl-5-chlorophe nyl)-pyrazine(C26H12Cl2N4O2C2H8O2,Mr=551.41),has been synthesized and characterized by LC-ESIMS,NMR,UV and IR spectroscopy as well as by X-ray single-crystal diffraction.The compound behaves as a substituted pyrazine.The hydrogen atoms on C(2) and C(3) are substituted by 2-pyridinyl,whereas those on C(1) and C(4) are substituted by 2-hydroxyl-5-chlorophenyl.It crystallizes in the monoclinic system,space group P21/c with a=8.9433(12),b=32.003(4),c=10.5209(18),β=111.199(2)°,V=2807.5(7)3,Z=4,Dc=1.305 mg/m3,F(000)=1144 and μ=0.094 mm-1.A total of 13235 reflections were collected in the range of 2.17～25.01o by using a phi and omega scan mode,of which 4923 were unique(Rint=0.0692) and 2872 observed reflections with Ⅰ > 2σ(Ⅰ) were used in the structure solution and refinement.     

Synthesis and Conformational Properties of the Sterically Crowded D3d-Symmetric all-trans Hexa(spirotetrahydrofuranyl)cyclohexane System

An unprecedented high barrier to ring inversion [Eq. (1)] prevents 1 from engaging in bifacial complexation with lithium ions. The X-ray crystal structure analysis of this hexaspiro compound corroborates the adoption of a cyclohexane chair with all six C−O bonds projected equatorially ( 1 -eq).     

卤化吡啶具有区域选择性的锂化反应与2,6-二甲氧基-3-溴-4-二苯基膦基吡啶的合成

在卤化吡啶的锂化反应的区域选择性研究基础上,以2,6-二甲氧基吡啶为原料,经溴化反应、邻位锂化反应和亲电取代反应制备了2,6-二甲氧基-3-溴-4-二苯基膦基吡啶,最终收率可达57．9％。