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41.
In Arbuzov-type reactions CFnCl3?nSCl reacts with ROPCl2 (R = CH3, C2H5) to give CFnCl3?nSP(O)Cl2 (n = 3,2,1,0). The corresponding reaction with CF3SeX (X = Cl, Br) produces CF3SeP(O)Cl2 in good yields only in the presence of catalysts such as SbCl5 or BCl3. Reactions between P4 and the sulfenylchlorides produce (CFnCl3?nS)xPCl3?n (n = 3,2,1 and x = 1,2). On heating CFn′ Cl3?n′ SP(O)Cl2 (n′ = 2,1,0) decompose to P(O)Cl3 and SCFn′ Cl2?n′. During this process fluorination of P(O)Cl3 to P(O)F3 by SCF2 is observed. A Cl/Br exchange between CFnCl3?nSP(O)Cl2 (n = 3,2) and PBr3 was proved 19F? and 31P-NMR-spectroscopically.Chemical and physical properties of the newly synthesized compounds will be discussed.  相似文献   
42.
Near-UV irradiation of structurally characterized [Re(I)(CO)3(1,10-phenanthroline)(Q107H)](W48F/Y72F/H83Q/Y108W)AzM(II) [Az = Pseudomonas aeruginosa azurin, M = Cu, Zn]/[Co(NH3)5Cl]Cl2 produces a tryptophan radical (W108*) with unprecedented kinetic stability. After rapid formation (k = 2.8 x 106 s-1), the radical persists for more than 5 h at room temperature in the folded ReAzM(II) structure. The absorption spectrum of ReAz(W108*)M(II) exhibits maxima at 512 and 536 nm. Oxidation of K4[Mo(CN)8] by ReAz(W108*)Zn(II) places the W108*/W108 reduction potential in the protein above 0.8 V vs NHE.  相似文献   
43.
[reaction: see text] The stereoselective aldol reaction of 3-silyloxyfurans with aldehydes in the presence of a Lewis acid is described. N-Bromosuccinimide (NBS)-mediated cyclization of the aldol product leads to the formation of the 2,7-dioxa-bicyclo[2.2.1]heptan-3-one ring system, which represents the formal product of hetero Diels-Alder reaction of the furan with the aldehyde.  相似文献   
44.
Zusammenfassung Es werden eine einfache Apparatur für nichtisotherme kinetische Messungen und Auswertungsverfahren mit Hilfe eines elektronischen Digitalrechners beschrieben. Die Meßmethode wurde an Diels-Alder-Reaktionen mit Nitrosoverbindungen erprobt; sie eignet sich gut zur raschen Ermittlung von Reaktionskonstanten nach Hammett.
Summary A simple apparatus is described for non-isothermal kinetic measurements, together with methods for interpreting the data using a digital computer. The method is tested for Diels-Alder reactions with nitroso compounds; it is useful for rapidty determining values of Hammett's reaction constants.


Herrn H. Ebert sei für die Hilfe beim Aufbau der Apparatur vielmals gedankt, der Deutschen Forschungsgemeinschaft für die großzügige Unterstützung durch Sachund Geldmittel, dem Leibniz-Rechenzentrum der Bayrischen Akademie der Wissenschaften für die Rechenerlaubnis am Digitalrechner TR 4.  相似文献   
45.
We prove that the number oft-wise balanced designs of ordern is asymptotically , provided that blocks of sizet are permitted. In the process, we prove that the number oft-profiles (multisets of block sizes) is bounded below by and above by for constants c2>c1>0.  相似文献   
46.
The Rhodium(III)-catalyzed thermal isomerization of 2-methylidenglutaric acid esters affords predominantly mixtures of cis/trans-2-methylglutaconic acid esters ( 2, 3 ) which upon slow distillation isomerize completely into the cis-esters ( 2 ). Saponification of 2 yields trans-2-methylglutaconic acid ( 5 ). Attempts to prepare the acid chloride of 5 produces 6-chloro-5-methylpyrone-2 ( 9 ) or 6-chloro-3-methylpyrone-2 ( 10 ) which react with anilines to N-substituted derivatives of trans-4-methylglutaconic acid amides ( 11 ). The thermal isomerizations of the respective esters are discussed in terms of 1,5-hydrogen shifts in their ester enol structures.  相似文献   
47.
Zusammenfassung Zur Messung der magnetooptischen Rotationsdispersion wird ein registrierendes Spektralpolarimeter verwendet, dessen Probenraum so groß ausgelegt ist, daß sich darin die zusätzlich notwendige Magneteinheit unterbringen läßt. Bei Untersuchungen an verdünnten Lösungen hat sich zur Kompensation der Magnetorotation des Lösungsmittels ein Doppelmagnet mit entgegengesetzten Magnetfeldeinrichtungen bewährt. Neben einer leicht durchführbaren Korrektur für unterschiedliche Dichten von Lösungsmittel und Lösung muß bei der Auswertung der gemessenen Spektren ein systematischer Fehler berücksichtigt werden, der durch Reflexionen innerhalb der Küvetten entsteht, und der Cotton-Effekte vortäuschen kann.
Summary For measuring the magnetic optical rotation a recording spectropolarimeter is used, the sample compartment of which is large enough to store the necessary magnet unit. When examining dilute solutions a double magnet having contrary magnetic field directions has proven to be effective to compensate for the magnetic rotation of the solvent. Besides a simple correction for the different densities of the solvent and the solution a systematic error has to be taken into consideration, which results from a reflection in the sample cell and may erroneously be taken for Cotton effects.


Wir danken der Stiftung Volkswagenwerk für die großzügige finanzielle Unterstützung dieser Arbeit.  相似文献   
48.
By optical interference and VUV spectroscopy the doublet system of SbI 5p 26s was investigated, so that now the hyperfinestructure of all 8 levels of 5p 26s (A- andB-splitting constants) are known. From the analysis we receive a spin-orbit parameter ζ5p =3,538(57) cm?1 and from the hyperfine-analysis single electron splitting constantsa 5p 01 =52.4(4.6),a 5p 10 =?1.6(7.3),a 5p 12 =72.3(2.3),a 6s 10 =91.7(4.1),b 5p 02 =?49.6(1.1) andb 5p 11 =30.4(3.2) (all values in mK). For all calculations in the fs- and hfs-analysis the 5p 26s 2 D 3/2 has to be excluded (see discussion). With the figures given above the quadrupole moment121 Q(5p 26s)=?0.44(3) barn was obtained. It is in good agreement with the121 Q(5p 3). For the core-polarization by the 5p electron in the innerfieldns-shells (n=1, 2, 3, 4, 5) and the unpaired 6s electron a field of +500(300) kG was obtained.  相似文献   
49.
Abstract Methyl-substituted psoralens (4'-(hydroxymethyl)-4,5',8-trimethylpsoralen and 4,5',8-trimethylpsoralen) are found to yield an ene product as well as the expected [2+2] cycloaddition product from photochemical reaction with simple olefins. As determined by absorbance, liquid chromatography-mass spectrometry and nuclear magnetic resonance, both products are formed at the pyrone side of the respective psoralen. The product distribution is dependent on olefin concentration as well as the nature of the olefin. In deoxygenated solutions, cyclic olefins form as much as 50% ene product, while unsubstituted straight-chain olefins form as little as 3%. In oxygenated solutions, the product distribution is strongly affected by singlet oxygen.  相似文献   
50.
The recent results of investigations involving the electrochemical formation of polymers containing fullerenes and studies of their properties and applications are critically reviewed. From a structural point of view, these polymers can be divided into four main categories including (1) polymers with fullerenes physically incorporated into the foreign polymeric network without forming covalent bonds, (2) fullerene homopolymers formed via [2+2] cycloaddition, (3) “pearl necklace” polymers with fullerenes mutually linked covalently to form polymer chains, and (4) “charm bracelet” polymers containing pendant fullerene substituents. The methods of electrochemical polymerization of these systems are described and assessed. The structural features and properties of the electrochemically prepared polymers and their chemically synthesized analogs are compared. Polymer films containing fullerenes are electroactive in the negative potential range due to electroreduction of the fullerene moieties. Related films made with fullerenes derivatized with electron-donating moieties as building blocks are electroactive in both the negative and positive potential range. These can be regarded as “double cables” as they exhibit both p- and n-doping properties. Fullerene-based polymers may find numerous applications. For instance, they can be used as charge-storage and energy-converting materials for batteries and photoactive units of photovoltaic cell devices, respectively. They can be also used as substrates for electrochemical sensors and biosensors. Films of the C60/Pt and C60/Pd polymers containing metallic nano-particles of platinum and palladium, respectively, effectively catalyze the hydrogenation of olefins and acetylenes. Laser ablation of electrochemically formed C60/M and C70/M polymer films (M=Pt or Ir) results in fragmentation of the fullerenes leading to the formation of hetero-fullerenes, such as [C59M]+ and [C69M]+.Dedicated to Professor Dr. Alan M. Bond on the occasion of his 60th birthday.  相似文献   
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