Eine semiempirische Gleichung zur Beschreibung des Lösungsmitteleinflusses auf Statik und Kinetik chemischer Reaktionen. Teil I

A model has been developed for calculating the enthalpy, entropy and free energy change associated with the creation of cavities in a liquid the size of which corresponds to the volume occupied by a solvent molecule. The molar enthalpy change H _cav equals the molar enthalpy of vaporization of the liquid, the free energy change G _cav is given by G _cav=–RT ln (V _m ·p _eq /RT) (V _m =molar volume,p _eq =equilibrium vapor pressure) and is related to the standard free energy of vaporization. This relationship provides an estimate of the free energy of cavity formation required to accomodate a substrate in the liquid. It has been shown, that the free energy of solvation of a substrate can be dissected into different contributions accounting for (1) the concentration dependence of partial molar free energy quantities, (2) the formation of holes in the solvent, (3) the existence of specific, short range solute-solvent interactions and (4) the dielectric polarization of the medium. Application of this concept leads to an equation of the general form G ^S –G ^R =a(DN ^S –DN ^R )+b(AN ^S –AN ^R )+c(G _vp ^oS –G _vp ^oR ), where G represents the free energy of reaction or activation,DN the donor number,AN the acceptor number and G _vp ^o the standard free energy of vaporization of a solventS and a reference solventR, resp.

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Automated carbohydrate synthesis to drive chemical glycomics

This feature article describes the development of the first automated solid-phase oligosaccharide synthesizer. A series of chemical challenges had to be addressed to accomplish this breakthrough and provide rapid access to oligosaccharides of biological significance. Accelerated synthesis of glycoconjugates promises to greatly impact the emerging field of glycobiology. Chemical glycomics uses synthetic carbohydrates and analogs to study their role in recognition, signal transduction pathways and other events of fundamental biomedical significance and shapes up to become the next major wave in biomedical research. The automated synthesis of a novel malaria vaccine candidate is discussed to illustrate the medical potential of chemical glycomics.     

Dimethylzinc-mediated addition of alkenylzirconocenes to alpha-keto and alpha-imino esters

[reaction: see text] Hydrozirconation of alkynes followed by in situ transmetalation to dimethylzinc and 1,2-addition to activated ketones and N-diphenylphosphinoylimines leads to tertiary allylic alcohols and amines in high overall yield. With 8-phenylmenthol as the chiral auxiliary, si-face attack proceeds in good to excellent diastereoselectivities.     

Untersuchung der Temperaturabhängigkeit derg ik -Tensoren von Polyäthyleneinkristallen

Zusammenfassung Es wurden die Kristallitgröße und die Änderungen der parakristallinen Gitterstörungen aus den Linienbreiten des Röntgenweitwinkeldiagramms von lösungskristallisiertem linearem Polyäthylen bei den Temperaturen 15°K, 73°K, 173°K und Zimmertemperatur bestimmt. Es wurde eine Zunahme der Gitterstörungen mit fallender Temperatur gefunden.

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Summary The crystallite size and the paracrystalline distortions in polyethylene single crystals were evaluated by the measurement of the linewidth in the X-ray wide angle diagram at four different temperatures (15°K, 73°K, 173°K and 297°K). An increase of the lattice distortions with decreasing temperature was found.

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Vorgetragen auf der Arbeitssitzung des Fachausschusses Physik der Hochpolymeren in der Frühjahrstagung 1970 des Regionalverbandes Hessen-Mittelrhein-Saar der Deutschen Physikalischen Gesellschaft in Darmstadt, 10.–13. März 1970.     

Die Schmelzdiagramme der Systeme CsN3/Zn(N3)2 und KN3/Zn(N3)2

The phase diagrams of the systems CsN₃/Zn(N₃)₂ and KN₃/Zn(N₃)₂ have been obtained employing the microscopic technique ofL. Kofler andA. Kofler. Within the system CsN₃/Zn(N₃)₂ three eutectics at 148°C, 142°C, and 210°C were found. Besides Cs₂Zn(N₃)₄, melting incongruently in the interval 153°C to 170°C, there exist two further compounds of the most probable composition Cs₃Zn₂(N₃)₇ and CsZn₂(N₃)₅, melting congruently at 170°C and 210°C, resp. In the system KN₃/Zn(N₃)₂ there exist two eutectics at 203°C and 172°C and two compounds, one of them, i.e. K₂Zn(N₃)₄, melting congruently at 206°C, the other one, with composition KZn₃(N₃)₇ or KZn₄(N₃)₉, melting incongruently at 210°C.

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Herrn Professor Dr.Heribert Grubitsch zum 70. Geburtstag gewidmet.     

Über einige Eigenschaften von Zinkphosphiten mit Berücksichtigung ihrer Wasserstoffbrückenbindung

Zinc phosphites ZnPHO₃·2.5 H₂O, Zn₂H₂P₃H₃O₉·H₂O, Zn₃H₄P₅H₅O₁₅·1.5 H₂O, ZnH₂H₂P₂H₂O₆ have been studied at higher temperatures and by X-rays and molecular spectroscopy. Hydrates ZnPHO₃·2.5 H₂O and Zn₂H₂P₃H₃O₉·H₂O, when heated, yield an anhydrous salt. Thermal decomposition of dihydrogen triorthophosphite and tetrahydrogen pentaorthophosphite leads, before oxidation of the anion, to a mixture of zinc phosphite ZnPHO₃ and dihydrogen diorthophosphite ZnH₂P₂H₂O₆ and then after loss of water of constitution dihydrogen diorthophosphite converts to zinc diphosphite ZnP₂H₂O₅. The results of the thermal decomposition study were confirmed by X-ray investigation. Anhydrous zinc dihydrogen triorthophosphite Zn₂H₂P₃H₃O₉ and zinc diphosphite ZnP₂H₂O₅ were hitherto unknown. Infrared spectra confirmed the existence of hydrogen bonding in all the phosphites studied and in the case of zinc phosphite ZnPHO₃·2.5 H₂O exhibited a symmetry decrease of the anion PHO₃ ^2– from the point group C_3v to C_s. In the crystal lattice of ZnPHO₃·2.5 H₂O hydrogen bonding by water molecules participates, with polyorthophosphites hydrogen bonding shares in the production of anions and in the case of their hydrates there is in addition hydrogen bonding by water molecules.

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Hydroxybromierung und Methoxybromierung von (Z)-Cycloocten

In addition totrans-2-bromocyclooctanol andtrans-1,2-dibromocyclooctane,cis-4-bromocyclooctanol,cis-1,4-dibromocyclooctane,trans-1,4-dibromocyclooctane, and (Z)-5-bromocyclooctene are obtained, when (Z)-cyclooctene is treated with N-bromosuccinimide in the presence of water. Similarly the methoxybromination of (Z)-cyclooctene gives transanular products.     

Interaction of dextran sulfates with positively and negatively charged silver bromide hydrosols

Summary The effects of dextran sulfates of different molecular weights and charge densities on the stability of positively and negatively charged silver bromide solsin statu nascendi have been studied by means of light scattering.The plots of scattering intensities of a positively charged sol against the concentration of the added dextran sulfates show one pronounced maximum, the position which is independent on the molecular weight of the polyelectrolyte used. The maximum shifts to lower polyion concentrations with dilution of the sol.The effect of polyanions on the stability of silver bromide sols of the same sign of charge were investigated as a function of molecular weight of the polymers, the sol concentration, the charge and the concentration of counterions, and the addition of methanol. Destabilization only occurred if sufficient amount of indifferent electrolyte was present in the system. However, the concentration of counterions necessary to produce a flocculation maximum was lower in the presence of the polyelectrolytes than in their absence. The results obtained were compared with the data on sols containing nonionic dextrans reported earlier.

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Zusammenfassung Der Einfluß der Dextransulfate von verschiedenen Molekulargewichten und Ladungsdichten auf die Stabilität der positiv und negativ geladenen Silberbromid-Solein statu nascendi wurden durch Lichtstreuung untersucht. Wenn die Intensitäten der Lichtstreuung eines positiv geladenen Silberbromid-Sols gegen die Konzentration der zugesetzten DextranSulfate aufgetragen werden, tritt ein ausgeprägtes Maximum auf, dessen Lage von dem Molekulargewicht des angewandten Polyelektrolyten unabhängig ist. Bei Verdünnung des Sols wird das Maximum zur niedrigeren Konzentration des Polyanions verschoben.Der Einfluß der Polyanionen auf die Stabilität der Silberbromid-Sole mit gleichem Ladungsvorzeichen wurde in Abhängigkeit von dem Molekulargewicht des zugesetzten Dextransulfats, der Solkonzentration, der Ladung und Konzentration der Gegenionen und dem Zusatz von Methylalkohol untersucht. Destabilisierung wird nur in Anwesenheit einer genügenden Menge von Neutralelektrolyten in den untersuchten Systemen beobachtet. Die Konzentration der Gegenionen, die ein Flockungsmaximum verursachen, ist immer niedriger als die kritische Koagulationsmenge derselben Ionen für das gleiche Sol in Abwesenheit von Makroionen. Die Resultate wurden mit den Wechselwirkungen der Silberbromid-Sole mit nichtionogenen Dextranen verglichen, und der Mechanismus der Flockung durch Polyelektrolyte wurde diskutiert.

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5 figures and 1 table

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Supported by the NSF Grant GP 42331 X.

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A part of the Ph.D. Thesis by David Lindsay.     

Field ionization mass spectrometry—IV. Isotopically labeled heptanals

The field ionization (FI) mass spectra of n-heptanal and a series of deuterium labeled analogs have been studied, with the objectives of initiating systematic investigations of reaction mechanisms of FI produced ions and to permit comprison with those found for other ionization processes. It is now recognized that FI ions have: (a) lower average internal energies and (b) shorter residence times than similar ions generated by electron-impact (EI), and the possibility exists of H/D-randomization occuring in ions formed by desorption from the emitter, by unimolecular decomposition close to the emitter and by either ‘fast’ or ‘slow’ metastable decompositions. In this study only the peak shifts of normal ions could be utilized; accurate mass measurements of all major ions revealed elemental compositions similar to EI. A site-specific McLafferty rearrangement gave the base peak at m/e 44 ([C₂H₄O]^+.), although the apparently complementary ion at m/e 70 ([C₅H₁₀]^+.) arose in a less specific process. Ions at m/e 43 ([C₃H₇]⁺) and 71 ([C₅H₁₁]⁺ 80%; [C₄H₇O]⁺ 20%) were apparantly generated without significant H/D-scrambling. Of special interest was the observation of the rearrangement ion at m/e 86 ([C₅H₁₀O]^+.) caused by loss of C-2 and C-3 as C₂H₄, as found for EI. It is concluded that at least in this system, decomposing molecular ions formed: (a) in the gas phase extremely close to the emitter and/or (b) on the emitter surface, have lifetimes sufficiently short to preclude complete H/D randomization. The results also provide evidence for common fragmentation mechanisms for heptanal molecular ions at both the low end and the high end of the energy distribution.     

Isomerisation in the chemistry of platinacyclobutane complexes

The platinacyclobutane complexes PtCl₂L₂(C₃H₅Me)], L  pyridine, CD₃CN, or tetrahydrofuran, exist as mixtures of isomers containing P$\text{tCH}{}_2\text{CHMeC}$H₂ or P$\text{tCHMeCH}{}_2\text{CH}{}_2$ groups in rapid equilibrium. Decomposition occurs in some cases to give [PtCl₂L(CH₃CH₂CHCH₂)]. Stereospecific skeletal isomerisation also occurs in metallocyclobutanes containing the groups P$\text{tCHRCHRC}$H₂  P$\text{tCHRCH}{}_2\text{C}$HR, when R  aryl further decomposition gives ν-allylplatinum complexes.