Linear, high molecular weight aryleneisopropylidene (AIP) polymers have been synthesized via Friedel-Crafts alkylation reactions. Monomers such as p-bis-2-chloroiso-propylbenzene condense readily with arylene compounds of high electron density such as naphthalene and diphenyl ether. Catalytic amounts of tritylhexafluoroarsenate catalysts in combination with aluminum chloride and nitrobenzene direct the synthetic reactions towards a pure AIP structure. Side reactions which give polyindane structures through dimerization of p-bis(2-chloroisopropyl)benzene are eliminated when the polymerization temperature is kept below ?20°C. The preferred solvents are chlorinated compounds. A wide range of structural modifications and properties can be obtained by varying the monomer combinations. Desirable physical properties of AIP polymers include clarity, rigidity, impact toughness, oxidative stability, and resistance to stress cracking. 相似文献
The effect of dimethyl sulphoxide on the anion-exchange behaviour of many metals m a methanolic system with hydrochloric acid was explored. Distribution coefficients for 26 elements were determined in a mixed solvent system of dimethyl sulphoxide-methanol-0.6M hydrochloric acid, in which the proportions of dimethyl sulphoxide and methanoi were varied. Lead(II) and silver(I) complexes are soluble in this system. Interesting effects were noted for gold(III), iron(III), molybdenum(VI) and uranium(VI). As a measure of the usefulness of the systems studied, 27 anion-exchange separations of two- to four-component mixtures of metal ions were carried out, each with quantitative results. 相似文献
Synthesis and Structure of Phosphinophosphinidene-phosphoranes tBu2P? P?P(Me)tBu21, tBu(Me3Si)P? P?P(Me)tBu22, and tBu2P? P?P(Br)tBu23 A new method for the synthesis of 1 and 2 (Formulae see ?Inhaltsübersicht”?) is reported based on the reaction of 5 with substitution reagents (Me2SO4 or CH3Cl). The results of the X-ray structure determination of 1 and 2 are given and compared with those of 3 . While in 3 one P? P distance corresponds to a double bond and the other P? P distance to a single bond (difference 12.5 pm) the differences of the P? P distances in 1 and 2 are much smaller: 5.28 pm in 1 , 4.68 pm in 2 . Both 1 and 2 crystallize monoclinic in the space group P21/n (Z = 4). 2 additionally contains two disordered molecules of the solvent pentane in the unit cell. Parameters of 1 : a = 884.32(8) pm, b = 1 924.67(25) pm, c = 1 277.07(13) pm, β = 100.816(8)°, and of 2 : a = 1 101.93(12) pm, b = 1 712.46(18) pm, c = 1 395.81(12) pm, β = 111.159(7)°, all data collected at 143 K. The skeleton of the three P atoms is bent (PPP angle 100.95° for 1 , 100.29° for 2 and 105.77° for 3 ). Ab initio SCF calculations are used to discuss the bonding situation in the molecular skeleton of the three P atoms of 1 and 3 . The results show a significant contribution of the ionic structure R2P? P(?)? P(+)(X)R2. The structure with (partially) charged P atoms is stabilized by bulky polarizable groups R (as tBu) as compared to the fully covalent structure R2P? P(X)? PR2. 相似文献
me3Si? CCl2?Sime2Cl (me ? CH3) läßt sich mit n-buLi (bu ? C4H9) bei–100°C (Lösungsmittel THF/Äther) in me3Si? CCl(Li)? Sime2Cl a überführen. das mit meJ me3Si? CClme? Sime2Cl bildet. Wird a in Abwesenheit eines Abfangreagenzes langsam erwärmt, so bildet sich unter Abspaltung von LiCl (Cl aus der SiCl-Gruppe) über eine reaktive Zwischenstufe des Bicyclobutans b . Die Struktur von b ist durch NMR-Untersuchung, Röntgenstrukturanalyse und Abbaureaktionen gesichert. Mit HBr bzw. CH3OH werden die Si? C-Bindungen der Dreiringe in b gespalten, so daß sich me3Si? CH2? C(Sime2X)2Sime3 (X ? Br, OCH3) bildet. Formation of Organosilicon Compounds. 85. Formation, Reactions, and Structure of 1,1,3,3-Tetramethyl-2,4-bis(trimethylsilyl)-1,3-disilabicyclo[1, 1, 0]butane me3Si? CCl2? Sime2Cl (me ? CH3) with n-buLi (bu ? C4H9) at –100°C (solvent: THF/ether) yields me3Si? CCl(Li)? Sime2Cl a , which forms me3Si? CClme? Sime2Cl with meI. By warming a slowly in absence of any trapping reagent the bicyclobutane b is obtained via a reactive intermediate under elimination of LiCl (Cl from the SiCl group). The structure of b is established by nmr investigations, X-ray structure determination and chemical derivatisation. 相似文献
The Formation of Disilylphosphino-Element Compounds of C, Si, P The reactions of (me3Si)2PLi · OR2 a (OR2 = 1 monoglyme or 2 THF; me = CH3) with CH3Cl, CH2Cl2, ClCH2CH2Cl and ClCH2? C6H5 give the compounds (me3Si)2Pme, (me3Si)2P? CH2? P(Sime3)2, (me3Si)2P? CH2CH2Cl, (me3Si)2P? CH2CH2? P(Sime3)2 and (me3Si)2P? CH2C6H5 respectively. In the same manner a reacts with me2SiCl2 in a molar ratio 1:1 to (me3Si)2P? Sime2Cl and in a molar ratio 2:1 to (me3Si)2P? Sime2? P(Sime3)2 b . The compound b decomposes to [me3SiP? Sime2]2 and (me3Si)3P at 220°C. In the reactions of a with ClP(C6H5)2 and ClPme2 the compounds (me3Si)2P? P(C6H5)2 and (me3Si)2P? Pme2, respectively, are obtained. a reacts with HgCl2 to (me3Si)2P? P(Sime3)2. (me3Si)3P can be cleaved with ClP(C6H5)2 and ClPme2 yielding (me3Si)2P? P(C6H5)2 and (me3Si)2P? Pme2, respectively. The 1H- and 31P-n.m.r. and mass spectroscopic data are reported. 相似文献
A simple, selective, and sensitive method for the simultaneous determination of anions (sulfate, nitrate, and chloride) and cations (sodium, ammonium, potassium, magnesium, and calcium) in acid rain waters was developed using ion-exclusion/ cation-exchange chromatography with conductimetric detection. A weakly acidic cation-exchange resin column (Tosho TSKgel OA-PAK-A) and a sulfosalicylic acid-methanol-water eluent was used. With a mobile phase comprising 1.25 mM sulfosalicylic acid in methanol-water (7.5:92.5) at 1.2 ml/min, simultaneous separation and detection of the above anions and cations was achieved in about 30 min. Linear calibration plots of peak area versus concentration were obtained over the concentration ranges 0-1.0 mM for anions (R=0.9991) and 0-0.5 mM for cations (R=0.9994). Detection limits calculated at S/N=3 ranged from 4.2 to 14.8 ppb for the anions and from 2.4 to 12.1 ppb for the cations. The reproducibility of retention times was 0.14-0.15% relative standard deviation (RSD) for anions and 0.18-0.31% for cations, and reproducibility of chromatographic peak areas was 1.22-1.75% RSD for anions and 1.81-2.10% for cations. The method was applied successfully to the simultaneous determination of anions and cations in aerosols transported from mainland China to central Japan, as determined by a meteorological satellite data analyzer. 相似文献
The search for new efficient sensitizers for photodynamic therapy (PDT) points to improve photophysical properties like absorption in the red region and singlet oxygen quantum yield as well as to control the localization of the sensitizer within the tumour cell. Depending on their physicochemical properties and their uptake mechanism, sensitizers can reach different intracellular concentrations and localize in different subcellular compartments. Moreover, the preferential localization of a sensitizer in target organelles, like mitochondria or lysosomes, could determine the cell death mechanism after PDT. This study aimed to investigate the influence of substitutions on dihydroxychlorins with regard to intracellular uptake, subcellular localization and cell death pathway. Moreover, the effect of a liposome-based delivery system was tested. The intracellular uptake was found to be strictly dependent on the sensitizer molecular structure and the means of its delivery. The most polar sensitizer in this study (compound 3) had, depending on incubation time, an intracellular concentration 2-8 times higher than the unsubstituted chlorin 1. All investigated photosensitizers localize predominantly in lysosomes but after longer incubation times weak fluorescence intensity was also detected in mitochondria and Golgi apparatus. The cell death pathway was found to be influenced by the sensitizer intracellular concentration and the applied light doses. In general, the increasing amphiphilicity of the sensitizer molecules is correlated with an increased sensitizer uptake and an increased rate of necrotic cells after irradiation. 相似文献
Formation of Organosilicon Compounds. 73. Reactions of C-chlorinated 1,3-Disilapropanes with CH3MgCl (Cl3Si)2CCl2 reacts with an excess of meMgCl (me = CH3) in Et2O (diethylether) forming (me3Si)22C?CH2 mainly besides Si-methylated 1,3-disilapropanes with CmeCl, CHCl, CH2 groups [6]. For investigating the mechanism of formation of the methylidengroup reactions were carried out with differently Si-methylated and Si-chlorinated 2-methyl-1-2-chloro-1,3-disilapropanes and 2,2-dichloro-1,3-disilapropanes. Whereas (me3Si)2CmeCl reacts neither with meMgCl nor with Lime. it forms (me3Si)2C?CH2 and (me3Si)2CmeH with Li or Mg resp. The reaction starts with the metallation to (me3Si)2CmeLi and (me3Si)2Cme(MgCl) resp., followed by elimination of LiH and HMgCl resp. with formation of (me3Si)2C?CH2. LiH and HMgCl resp. reduces (me3Si)2CmeCl to (me3Si)2CmeH. This mechanism is supported by the reactions of (me3Si)2CCl(CD3). The Si-chlorination increases the reactivity of the CmeCl group and the created C?CH2 group favours Si-methylation. The CCl2 group is more reactive than the CmeCl group; (me3Si)2CCl2 already forms the methyliden group with meMgCl in Et2O via the not isolated intermediate (me3Si)2CCl(MgCl). which prefers the methylation to (me3Si)2Cme(MgCl). The n.m.r. data of the investigated compounds are given. 相似文献
3-Substituted 1-iminopyridinium ylides 1 undergo photo-induced ring enlargement to 1H-1,2-diazepines. With strongly electron-withdrawing substituents the ring expansion process is regiospecific and leads exclusively to 4-substituted 1 H-1, 2-diazepines. Weak electron-donating substituents, like a methyl group and halogen atoms, do not have any directing effect since both 4- and 6-substituted 1 H -1,2-diazepines are obtained. With strong electron-donating substituents no diazepines are formed; instead one observes photo-induced isomerization to the 2-aminopyridine derivatives, the process being non-regiospecific. Regiospecific photo-induced ring expansion processes are explained in terms of a simple HMO model. 相似文献