Synthesen und chemisches Reaktionsverhalten von neuen Azapseudophenalenonen,Azapseudophenaleniumsalzen und ihren Fulvenen sowie Fulvalenen

Alkylation of the aza-pseudophenalenone1 with trialkyloxoniumtetrafluoroborates yield the azapseudophenaleniumsalts2 a,2 b, reactions with C-nucleophiles the compounds3 a 3 e, the dihydro-azapseudophenalenone4 reacts with malodinitrile-sodium to5,1 b and1 d with tetrachlorocyclopentadiene to the fulvalenes6 a,6 b,1 b was olefinated withtert. butyl-cyano-ketene to theZ-isomer7.

Meinem lieben Kollegen und Freund, Herrn Prof. Dr.Werner Heimann, Karlsruhe, mit herzlichen Wünschen zum 70. Geburtstag gewidmet.     

Synthesis of light-sensitive arenesulfonylazido polycarboxylic acids

Several light-sensitive arenesulfonylazido polycarboxylic acids were synthesized by a one-step reaction of a polymeric anhydride with a light-sensitive monofunctional alcohol, or by the reverse reaction, i.e., reaction of a polymeric alcohol with a light-sensitive monofunctional anhydride. The polycarboxylic acids are soluble in polar organic solvents and in aqueous base. Neutralization of part of the carboxyl groups gives rise to the formation of water-soluble polymers. Coreaction of poly(maleic anhydride-co-methyl vinyl ether) with 2-hydroxyethyl 4-sulfonylazidocarbanilate and 2-hydroxyethyl trans-2,5-dimethoxystilbene-4′-carbamate produces a light-sensitive polycarboxylic acid with “built-in” sensitizer.     

(Perhalogenmethylthio)heterocyclen. X. Säurekatalysierte Substitutionen an (Perchlorfluormethylthio)pyrrolen und deren agrobiologische Wirkung

(Perhalomethylthio)heterocycles. X

1 IX. Mitt.: s. [1].

. Acid-catalyzed substitutions on (perchlorofluoromethylthio)pyrroles and their agro-biological activities In the presence of C₄F₉SO₃H the (perhalomethylthio)pyrroles 1a–c react with Cl_3?nF_nCSCl (n = 1–3) to give mixtures of the 2,5- and 2,4-disubstituted pyrroles 2a–f and 3a–h . 2a and 3a react with CF₃SCl (catalyst CF₃SO₃H) yielding 2,3,5-tris (trifloromethylthio)pyrrole ( 4a ), which under similar conditions reacts further to give 2,3,4,5-tetrakis (trifluoromethylthio)pyrrole ( 5 ). As a by-product during the conversion of 3a to 4a 2,3,4-tris (trifluoromethylthio)pyrrole ( 4b ) is formed. The pyrroles 2a , 4a and 5 form the mercury salts 6a–c ; compound 5 yields also a silver salt 7 . The ¹H- and ¹⁹F-NMR. spectra are discussed and the agro-biological properties of the compounds investigated.     

Etude de la fragmentation de derives de L'uracile et de la thymine par Spectrometrie de masse

Original mass spectra of uracil and thymine derivatives are presented with the corresponding fragmentation schemes. In the first series of spectra, the fragmentations of thymine derivatives, including ¹⁴C-2-thymine, dimers, and bromo thymines, confirm the basic retro Diels-Alder mechanism. The second series includes dihydro 5,6-derivatives of uracil (hydroxy and bromo substituents). The behaviour of these molecules is quite different; they are more sensitive to the substituents and a part of the fragmentation is often explained by protonated molecular ions.     

β-Polycarbonylverbindunge, 5. Mitt.: 1,3-Diaminobenzole durch Acylierung von Di-enaminen

Zusammenfassung Die Reaktion von 1,3-Bis-dimethylamino-1,3-dienen mit Säurechloriden zu substituierten 1,3-Diaminbenzolen wird beschrieben.

---

The reaction of 1,3-bis-dimethylamino-1,3-dienes with acyl chlorides to substituted 1,3-diaminobenzenes is described.

---

---

Herrn Prof. Dr.L. Schmid zum 70. Geburtstag in Verehrung gewidmet.

---

4. Mitt.:Ulrich Schmidt undM. Schwochau, Tetrahedron Letters 1967, 4491.     

Übergangsmetall-thioketen-komplexe: VII. Erzeugung eines vinyliden-liganden aus einem thioketen durch schwefelabspaltung

The thioketene iron cluster (CH₃)₄C₆H₆CS(PPh₃)₂(CO)₄Fe₂S (I) reacts with thioketene in excess quantitatively to a vinylidene complex, as confirmed by X-ray analysis.     

Reply to the ‘Comment on “Uncommon structural and bonding properties in Ag16B4O10” by A. Lobato,Miguel Á. Salvadó, and J. Manuel Recio,Chem. Sci., 2021, 12, DOI: 10.1039/D1SC02152D

Where are the excess electrons in Ag₁₆B₄O₁₀?

Ag₁₆B₄O₁₀ features an exotic scheme of chemical bonding and extends the growing family of subvalent silver oxides. These findings constitute a new general and intrinsic facet of the chemistry of silver, which has not been fully understood, yet, and definitely deserves to be analysed from different perspectives. Against this background, we distinctly appreciate the efforts made by A. Lobato, Miguel Á. Salvadó, and J. Manuel Recio (LSR) in studying these phenomena at the example of the title compound.¹ While the computational results presented in the Comment article well comply with those published in our original paper,² the interpretations follow different routes. Whereas LSR focus on the analogy of pattern of the Electron Localization Function (ELF) in position space in the title compound with those found in elemental silver, we interpreted the electronic structure of Ag₁₆B₄O₁₀, both in position and reciprocal space, also considering the interactions between cationic and anionic partial structures.