Notiz über die Reaktion zwischen Phosphortrichlorid und Schwefelwasserstoff

Notice on the Reaction between Phosphorus Trichloride and Hydrogen Sulfide The reaction between phosphorus trichloride and hydrogen sulfide in the presence of a base yields P₄S₃ and [PS₂Cl₂]^? besides other products. A reaction scheme is proposed.     

Notiz über die Kernresonanzspektren von trifluormethyl-substituierten Naphthalinderivaten

The proton and fluorine NMR. spectra of 25 trifluoromethyl substituted naphthalene derivatives have been analysed. The proton chemical shifts of the trifluoromethyl naphthylamines and naphthols have been correlated with calculated π-electron charge densities (PPP SCF).     

Über die Natur der Übergangsmetall-Kohlenstoff-σ-Bindung. VIII. Über die Reaktion von 3d-Metallhalogeniden mit Thioanisolyllithium

On the Nature of the Transition Metal Carbon-σ-Bond. VIII. Reaction of 3d-Metal Halides with Thioanisolyl Lithium Reaction of CoBr₂ · 2 THF with PhSCH₂Li/N(CH₂CH₂)₃N (TED) results in the formation of the thiophenolato complex LiCo(SPh)₃ · TED · 3.5 THF (I) with ethylene, propylene, and small amounts of cyclopropane being liberated. The constitution of I follows from the results of the elemental analysis, the effective magnetic moment (μ_eff. = 4.41 B.M.), and the reaction with acids and HgCl₂ to give PhSH and PhSHgCl, respectively. I could also be isolated by comparison synthesis from CoBr₂ · 2 THF and LiSPh/TED. Other 3d-metal halides MX_n · xTHF (M = Ti, V, Mn, Fe, Ni; X = Cl, Br) also react very easily with thioanisolyl lithium to form thiophenolato compounds.     

Favorskii-Reaktion von enolisierbaren Cyclobutanonen: Abhängigkeit der Stereoselektivität von der Abgangsgruppe,der Temperatur und dem Lösungsmittel

Dependence of the Stereoselectivity on the Leaving Group, the Temperature and the Solvent in the Favorskii-Reaction of Enolisable Cyclobutanones The base-induced contraction of enolisable 2-halocyclobutanones is often not stereoselectiv. The cis/trans-isomer ratio in the cyclopropanecarboxylic acid 9 derived from 2,4-cis-substituted cyclobutanones 7 depends on the nature of the leaving group. In addition, the choice of the base, the temperature and the solvent can profoundly affect the stereoselectivity of the Favorskii-reaction. The use of the p-bromophenylsulphonyloxy group as leaving group and an inhomogenous reaction medium leads exclusively to cis-carboxylic acid 9 .     

Notiz über die Photoelektronen-Spektren des Nortricyclens und des Triasterans

The photocelectron spectra of nortricyclene (=tricyclo[2.2.1.0^2,6]heptane) and of triasterane (=tetracyclo[3.3.1.0^2,8.0^4,6]nonane) have been recorded and a tentative assignment of the bands has been put forward on the basis of MINDO/2 SCF calculations.     

Über die Reaktion von Alkalihexafluorosilicaten mit Aluminiumoxid

On Reactions of Alkali Hexafluorosilicates with Aluminum Oxides The reaction of Na- and K-hexafluorosilicates and α- or γ-Al₂O₃ has been investigated. Final reaction products are fluoroaluminates and alumosilicates. The reaction mechanism has been discussed. Influence of reaction parameters like time, temperature, layer thickness, and the effect of admixtures (fluorides, SiO₂) have been regarded. Tablet-reactions show the introduction of reaction by Si? F species.     

Notiz über die Massenspektren cyclischer Ketale

The mass spectral behavior of substituted 2-phenyl-1, 3-dioxolanes has been studied. In the spectra of this group of compounds the most important peak is m/e 105 for which benzoylonium structure b is proposed. Another interestingion in the mass spectra of these compounds is c . This ion is protonated benzoic acid.     

Über die Reaktion von Protein-SH-Gruppen mit 4-Hydroxypentenal

Zusammenfassung 4-Hydroxy-2-pentenal (HPE) reagiert mit den schnellen SH-Gruppen von Proteinen unter Addition der SH an die Doppelbindung desHPE. Das an das Protein gebundeneHPE wird nach Behandlung mit 2.4-Dinitrophenylhydrazin quantitativ bestimmt, der Verlust an SH-Gruppen mitEllmans Reagens. Zwischen beiden Werten besteht ein linearer Zusammenhang.Die Reaktion zwischenHPE und Protein-SH verläuft über ein reversibles Gleichgewicht. Bei Zugabe eines zweiten Proteins, dessen SH-Gruppen gegenüberHPE reaktiver sind, trittHPE von den SH-Gruppen des ersten auf die des zweiten Proteins über. Dies wird am Beispiel des Addukts ausHPE und Serumalbumin, bzw. -Lactoglobulin nach Zugabe von Glyceraldehydphosphatdehydrogenase gezeigt, wobei der Verlust der Enzymaktivität den Transfer desHPE auf die funktionellen und hochreaktiven SH-Gruppen des Enzyms anzeigt.

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Reaction of protein SH-groups with 4-hydroxy-2-pentenal

4-Hydroxy-pentenal (HPE) reacts with fast SH-groups of proteins (PSH) by addition of SH to the double bound ofHPE. On the one hand, by means of treatment with 2.4-dinitrophenylhydrazine the formed protein bound 2.4-dinitrophenylhydrazones can be measured spectrophotometrically, allowing thus a quantitative estimation of protein boundHPE. On the other hand, the estimation ofPSH before and afterHPE-treatment of the protein yields the moles of SH consumed thereby. With nativeGAPDH, ALD, andRSA, larger differences between the amount of protein boundHPE andDTNB estimated loss ofPSH are observed, good coincidence with native ovalbumin and proteins with reduced S–S-bridges. Thus, the differences named above are explained with the assumption that in some native proteins SH-groups can react somewhat differently withHPE orDTNB.The reaction betweenHPE andPSH is characterized by a reversible equilibrium. After addition of a second protein the SH-groups of which having the higher reactivity towardsHPE, a transfer ofHPE occurs from the first to the SH-groups of the second protein. This is demonstrated withHPE-serum albumin adduct (orHPE-lactoglobulin adduct) after addition of active glyceraldehydephosphat-dehydrogenase whereby the loss of enzyme-activity indicates the transfer ofHPE to the functional and highly reactive SH-groups of the enzyme.

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Mit 5 Abbildungen     

Über Chalkogenolate. 146. Asymmetrische Derivate der Kohlensäure mit Elementen der IV. Hauptgruppe. Notiz über Silbermonomethylcarbonat

On Chalcogenolates. 146. Asymmetric Derivatives of Carbonic Acid with main Group IV Elements. Notice of Silver Monomethyl Carbonate The esters of carbonic acid have been prepared by different methods. The compounds were characterized by means of infrared, nuclear magnetic resonance (¹H and ¹³C), and mass spectra. Synthesis and properties of unstable Ag[O₂C? OCH₃] are described. The infrared spectrum is given.