Ag(PPh3)nX(n=1,2,3；X=Cl,Br,I)的电化学合成

银配合物;;三苯基膦;电合成;Ag(PPh3)nX(n=1;2;3；X=Cl;Br;I)的电化学合成     

两种基于硫醇配体的银(Ⅰ)配合物的合成、表征和晶体结构

通过AgCl、PPh₃和MBT以1:2:1的物质的量之比反应得到2种不同的配合物[AgCl(PPh₃)₂(BTZT)]·CH₃OH (1)和[AgCl(PPh₃)₂ (BTZT)]₂ (2)(PPh₃=三苯基膦;MBT=2-巯基苯并噻唑;BTZT=苯并噻唑-2-硫酮)(其中2已报道)。配合物[AgBr(PPh₃)₂(BTZT)]·CH₃OH (3)和[AgBr(PPh₃)₂(BTZT)]₂ (4)改用AgBr以相似的反应获得(其中4已报道)。通过红外光谱、元素分析、核磁共振氢谱、X射线单晶衍射、荧光光谱对配合物1和3进行了分析和表征。我们发现在不同的化学环境中,MBT配体可以转化为BTZT配体,原因是其具有化学活性基团。荧光光谱表明1和3的发射峰均源于配体中的π-π^*跃迁。     

Synthesis and Crystal Structure of 2-(4''-Methylphenoxy)-5,8,9-trimethyl-3-phenyl Thieno[3'',2'':5,6]pyrido[4,3-d]pyrimidin-4-(3H)-one Hydrochloride

The title compound 2-(4′-methylphenoxy)-5,8,9-trimethyl-3-phenyl thieno[3′,2′:5,6]pyrido[4,3-d]pyrimidin-4(3H)-one hydrochloride (C26H23Cl4N3O2S, Mr = 583.33) has been deter- mined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 14.8442(11), b = 11.5131(8), c = 17.2010(13) (A), β = 113.7250(10)o, V = 2691.3(3) (A)3, Z = 4, Dc = 1.440 g/cm3, S = 1.094, μ = 0.547 mm-1, F(000) = 1200, the final R = 0.0571 and wR = 0.1458. X-ray analysis reveals that the title compound combines with a molecule of dichloromethane by an intramolecular hydrogen bond. The thienopyridine ring is almost coplanar, and the dihedral angle between the thiophene plane and the pyridine plane is 0.6o.     

31P Solid state NMR study of structure and chemical stability of dichlorotriphenylphosphorane

Solid state ³¹P NMR spectroscopy was used to examine, monitor and quantify the compound integrity of the chemical reagent dichlorotriphenylphosphorane. Comparison was also made with solution ³¹P NMR spectra which showed that this highly reactive species could be observed in dry benzene prior to conversion to the hydrolyzed product. This is the first reported solid state NMR study of the stability and reactivity of dichlorotriphenylphosphorane and the first account of its observation and comparison in the solution state. In the solid state, the ionic and covalent forms for dichlorotriphenylphosphorane were observed along with hydrolyzed products, however, the degree of hydrolysis was dependent upon the rotor packing conditions. Calculation of the relative percent composition of dichlorotriphenylphosphorane with hydrolyzed product was made for samples prepared in air versus under nitrogen atmosphere. This information was critical in adjusting the amount of reagent used in chemical development syntheses and scale up laboratories. All hydrolyzed products were identified, based upon chemical comparisons with spectra of pure materials. Copyright © 2009 John Wiley & Sons, Ltd.     

2,15-十六二酮的合成

以廉价易得的10－十一碳烯酸为原料经两步反应合成了人工合成麝香酮的关键中间体2,15－十六二酮。     

TRIPHENYLPHOSPHINE-MEDIATED CHEMOSELECTIVE SYNTHESIS OF FUNCTIONALIZED SPIRO-IMIDAZOL-4-ONES

Stabilized phosphoranes, obtained from the three-component reaction between dialkyl acetylenedicarboxylates and spiro-hydantoins in the presence of triphenylphosphine, undergo a smooth intramolecular Wittig reaction in boiling toluene to produce functionalized spiro-imidazol-4-ones in good yields.     

Efficient Synthesis of Trialkyl (E)‐3‐{3‐Oxo‐2‐3,4‐dihydro‐2‐(1H)‐quinoxalinylidene}‐prop‐1‐ene‐1,2,3‐tricarboxylates

The reaction of dialkyl acetylenedicarboxylates with alkyl 2‐[3‐oxo‐3,4‐dihydro‐2(1H)‐quinoxadinylidene]ethanoates in the presence of triphenylphosphine leads to trialkyl (E)‐3‐{3‐oxo‐2‐3,4‐dihydro‐2‐(1H)‐quinoxalinylidene}‐prop‐1‐ene‐1,2,3‐tricarboxylates in good yields.     

Three-Component Reaction of Triphenylphosphine,Dialkyl Acetylenedicarboxylates,and Heterocyclic Rings and the Related Iminophosphoranes

Crystalline phosphorus ylides are obtained in excellent yields from the 1:1:1 addition reaction of triphenylphosphine, dialkyl acetylenedicarboxylate, and NH acids, such as 2-aminothiazole and 2-aminobenzothiazole. These stabilized phosphoranes undergo a smooth intramolecular reaction in boiling toluene to produce aryliminophosphoranes in excellent yields.     

SYNTHESIS OF HIGHLY ELECTRON-POOR ALKENES FROM IN SITU GENERATED STABILIZED PHOSPHORUS YLIDES AND NINHYDRIN VIA INTERMOLECULAR WITTIG REACTION

Protonation of the highly reactive 1:1 intermediates, produced in the reaction between triphenylphosphine and dialkyl acetylenedicarboxylates, by alcohols leads to vinyltriphenylphosphonium salts, which undergo Michael addition reaction with conjugate base to produce the corresponding stabilized phosphorus ylides. Intermolecular Wittig reaction of the stabilized phosphorus ylides with ninhydrin leads to the corresponding, highly electron-poor alkenes.