Crystal and molecular structure of the cycloaddition product between maleic anhydride,cyclopentadiene, and 1,2-bis(dibromomethyl)benzene as DMF solvate (1∶2)

Crystal structure determination reveals that the unknown cycloaddition product between maleic anhydride, cyclopentadiene, and 1,2-bis(dibromomethyl)benzene has a nona-cyclic centrosymmetric structure. The compound was studied as DMF solvate (12). There is no significant intermolecular interaction between the title molecule and the DMF. Packing is in layers for both molecular species. A possible mechanism of formation of the title compound is discussed.     

carbon-carbon bond formation between 1,3-dienes and electron deficient alkenes

1,3-Dienes and electron deficient alkenes are coupled in a one pot carbon-carbon bond formation reaction under mild conditions.     

Säurekatalysierte Dienon-Phenol-Umlagerungen von 6-Propargyl-6-methyl-cyclohexa-2,4-dien-1-onen; ladungskontrollierte,aromatische [1s, 2s]- und [3s, 4s]-sigmatropische Reaktionen

The acid catalysed dienone-phenol rearrangement of methyl substituted o-propargyl-cyclohexadienones (scheme 3) was investigated. The rearrangements were carried out in acetic anhydride containing about 1⁰/₀₀ sulfuric acid. Under these conditions acetoxy benzenium ions are formed as intermediates. These then undergo charge-controlled [3s, 4s]- and [1s, 2s]-sigmatropic rearrangements. Thus, the [3s, 4s]-process leads to the formation of the corresponding allenyl-phenol acetates ( 19 , 21 , 23 , 25 , 28 , 30 ) whereas the [1s, 2s]-process yields propargyl-phenol acetates ( 20 , 22 , 24 , 26 , 29 ), respectively (cf. scheme 4).     

Zur Chemie der Pyrrolpigmente, 56. Mitt.

From an investigation of the ICD of bilatrienes-abc and 2,3-dihydrobilatrienes-abc induced by mixtures of CCl₄ with (+)-cis-Pinane, (–)-lactic and (+)-tartaric acid esters it is concluded that specific interactions between chromophore and the chiral reagents afford a partial resolution of the labile racemate of helices. Attaching chiral residues covalently to the chromophore induces very low resolution of the same kind in case of apolar ligands like a cholesteryl-residue. However, with polar ligands as in the case ofBoc-lysyl derivatives enantiomeric excesses up to 90% are achieved depending on the solvent used.

Herrn Prof. Dr.Karl Schlögl zu seinem 60. Geburtstag gewidmet.     

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.