Über die Synthese des Muscaflavins. Vorläufige Mitteilung,

Synthesis of muscaflavin A biomimetic type synthesis of the yellow dihydroazepine amino acid 5 isolated from fly agaric is achieved starting with carboxypyridyl alanine derivatives.     

Über Diels-Alder-Reaktionen des C60-Fullerens Vorläufige Mitteilung

On Diels-Alder Reactions of the C₆₀-Fullerene We report on the regioselective [4+2] cycloaddition of Buckminsterfullerene C₆₀( 1 ) at room temperature with 2,3-dimethylbuta-1,3-diene and with the monoterpene 7-methyl-3-methylideneocta-1,6-diene (= myrcene) and on the spectroscopic characterization of the corresponding crystalling monoadducts 2 and 3 . According to these experiments, 1 acts as a reactive dienophile, which can be functionalized regioselectively under mild and controlled conditons.     

Über die Konstitution von Loroglossin. Vorläufige Mitteilung

The Constitution of Loroglossine. Loroglossine, a characteristic constituent of orchids, is shown to be bis-[4-(β-D -glucopyranosyloxy)-benzyl]-(2 R, 3 S)-2-isobutyl-tartrate ( 1 ). Hydrolysis and esterification gave 1 mol-equiv. of dimethyl (+)-2-isobutyl-erythro-tartrate ((+)-3) and 2 mol.-equiv. of a glucoside which, after acetylation, gave 4 , identical with a synthetic sample. The erythro configuration of (+)- 3 by oxidation of isobutyl-maleic acid with osmium tetroxide and subsequent esterification. The absolute configuration of (+)- 3 was based on Horeau experiments and NMR. data of the diastereomeric mixture of its esters 7 and 8 with S (+)- and R (?)-α-phenylbutyric acid respectively.     

Zur Stereochemie der thermischen Fragmentierung von Hydrazonderivaten substituierter N-Amino-aziridine. Vorläufige Mitteilung

The thermally induced fragmentations of the hydrazones derived from phenylglyoxal and the diastereomeric 2,3-diphenyl-1-amino-aziridines and 2,3-dimethyl-1-amino-aziridines proceed with high stereospecificity.     

Über die relative Reaktivität von Nucleophilen. Vorläufige Mitteilung

For a number of nucleophiles L an approximate linear correlation between the logarithms of the stability constants of methylmercury-complexes of L and the nuclear spin-spin-coupling constants J of Ch₃HgL was found.     

Über ein neues Verfahren zur Herstellung von. Acetylenverbindungen. Vorläufige Mitteilung

A new method for the preparation of acetylenes by reating α-halogeno- or α-sulfonyloxyketones with p-toluenesulfonylhydrazine is reported.     

Nickel-katalysierte Isomerisierung von Butadien-Hydrazon-Misch-Oligomeren. Vorläufige Mitteilung

Nickel-catalysed Isomerization of Unsaturated Azocompounds Unsaturated azocompounds, produced by the nickel-catalysed reaction of butadiene with hydrazones, can be isomerized in presence of the same nickel catalyst. The influence of nickel concentration, temperature and structure of the azocompound on this rearrangement is described.     

Über Enolderivate der Chlorophyllreihe. Darstellung von 132,173-Cyclophäophorbid-enolen. Vorläufige Mitteilung

Enol derivatives in the chlorophyll series. Preparation of 13²,17³-cyclopheophorbide enols 13²,17³-Cyclopheophorbide enols have been prepared as model systems for studying the effect of ring E enolization upon the properties of chlorophyll derivatives.     

Synthese makrocyclischer Lactone durch Ringerweiterung. Vorläufige Mitteilung

Synthesis of Macrocyclic Lactones by Ring Enlargement Reaction Treatment of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) prepared by Michael addition of 2-nitrocyclohexanon and acrylaldehyde with methyltri (2-propoxy)tita-nium yielded a mixture of 2 and 3 which was converted into 6-nitro-9-decanolide ( 4 ).     

Photoelektron-Spektren von Cycloalkenen und Cycloalkadienen. Vorläufige Mitteilung

The photoelectron spectra of cis-cycloalkenes (with three to ten carbon atoms in the ring), of three isomeric, non-conjugated cyclodecadienes, and of cis, cis, -1, 3-cycloalkadienes (with five to eight carbon atoms in the ring) have been recorded. The essential features of their π-bands and of the first σ-bands are briefly discussed.     

Synthesen Makrocyclischer Lactone durch Ringerweiterung. Vorläufige Mitteilung

Syntheses of Macrocyclic Lactones by Ring Enlargement Reaction A general method is given for the synthesis of macrocyclic lactones by ring enlargement of 2-nitrocycloalkanones by four ring members. By this procedure 2-nitrocyclooctanone ( 1 ) is transformed to 8-oxo-dodecan-11-olid ( 5 ) in an overall yield of 63,5% and 2-nitrocyclododecanone to 12-oxo-hexadecan-15-olid with 60% yield.     

Photochemisches Verhalten von 3,4-Diarylsydonen. Vorläufige Mitteilung

3, 4-Diphenyl-sydnone ( 1a ) and 3-p-tolyl-4-phenyl-sydnone ( 1b ) on irradiation with a mercury high-pressure lamp in pyrex vessels yield 2,4,5-triphenyl- ( 3a ) and 2-p-tolyl-4,5-diphenyl-1,2,3-triazole ( 3b ), respectively. Irradiation of 1a and 1b in the presence of dimethyl acetylene-dicarboxylate or indene leads to the formation of the pyrazoles 4a and 4b and the Δ²-pyrazolines 5a and 5b , respectively. Reactive intermediates of the photoreaction of 1a and 1b seem to be the diazirines 2a and 2b , which open to give the 1,3-dipolar structures 8a and 8b .     

Synthese yon 2,6-Diencarbonsäuren Vorläufige Mitteilung

Through sequential Claisen- and Cope rearrangements the chainlengthening of allylic alcohols by one isoprene unit was achieved. Treatment of (E)-1a first with lithium N-cyclohexyl-N-isopropylamide at ?70°, followed by trimethylsilylchloride and warming up to room temperature yielded after work-up 3a (R = H), which rearranged at 156° in high yield to (E/Z)-4a. An analogous reaction sequence transformed 6 to 8. Choosing lithium N-methylanilide as a base (E/Z)-9 was selectively rearranged to 12, which was converted to the Cecropia juvenile hormone precursor (E/Z)-4b.     

Identifizierung von sechs Komponenten des Spurpheromons der Ameisenart Lasius fuliginosus. Vorläufige Mitteilung

Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and dodecanoic acid are components of the trail pheromone of the ant species Lasius fuliginosus. The acids were extracted from the contents of the rectal ampullae and identified by the mass spectra and gas chromatographic retention times of the corresponding methyl esters.     

Automerisierung von 1,3,5,5-Tetramethylcyclohexa-1,3-dien. Vorläufige Mitteilung

1,3,5,5-Tetramethylcyclohexa-1,3-diene, specifically deuterated in all positions except the gem.-dimethyl groups ( 11 ), was synthesized and found to undergo a rearrangement in the gas phase at 560°, which leads to a statistical distribution of the 6 hydrogen atoms to all 16 positions. This shows that the title compound ( 2 ) automerizes under these conditions and that the reaction proceeds via a series of ring openings (to 5 ) followed by degenerate [1,7]-H-shifts and rig closures (back to 2 ) rather than via [1,5]-CH₃-shifts. It is suggested that the previously studied rearrangement of 5,5-dimethylcyclohexa-1,3-diene ( 1 ) to 1,5-dimethylcyclohexa-1,3-diene ( 3 ) takes its course by the same reaction pathway.     

1, 6-Addition von Chlorsulfonylisocyanat. Vorläufige Mitteilung

A 1, 6-addition of sulfonyl chloride isocyanate to 5, 7-dimethyl-8-methylidene-tricyclo[3.2.1.0^2,7]oct-3-en-6-one ( 1 ) produced the new tricyclic skeleton of 4a, 6-dimethyl-2, 5-dioxo-2, 3, 4a, 5, 6, 8a-hexahydro-1H-6, 4-methenoquinoline-1-sulfonyl chloride ( 2 ). The structure of the new aza-tricyclic species has been elucidated by X-ray analysis.     

Über die Reaktion 1,2-disubstituierter Norbornane mit Dinatriumtetracarbonylferrat(-II). Vorläufige Mitteilung

Reductive elimination at 1,2exo-diiodonorbornane ( 6 ) was induced by Collman's reagent. Surprisingly, 1,2endo-diiodonorbornane ( 9 ) and 1-iodo-2endo-trifluoromethylsulfonyloxy-norbornane ( 10b ) lead only to reactions of the substituent in 2-position. Mechanistic aspects are related to the reactions of monosubstituted iodonorbornanes with Collman's reagent.     

Ein symmetrisches Tetrasulfolenoporphyrin als Reaktivbaustein,Vorläufige Mitteilung

A Symmetrical Tetrasulfolenoporphyrin as Reactive Building Block The efficient preparation of the symmetric tetrasulfolenoporphyrin 1 is reported, which shows good solubility in a variety of solvents. In 1 , four sulfone groups that symmetrically bridge the eight methylene groups in β‐position at the pyrrole rings provide four sulfolene (=2,5‐dihydrothiophene 1,1‐dioxide) units which are prone to cleavage by thermally induced extrusion of sulfur dioxide. The tetrasulfolenoporphyrin, accordingly, is indicated to lend itself to specific and multiple refunctionalization by the replacement of the sulfone groups by other functionalities in SO₂ extrusion/cycloaddition sequences. The predicted reactivity and the potential of a zinc complex of the tetrasulfolenoporphyrin as a reactive porphyrin module (see 5 b ) is tested in exploratory experiments. To this end, thermolysis of the tetrasulfolenoporphyrinatozinc 5 b in dichlorobenzene solution (at 140°) and in the presence of [5,6]fullerene‐C₆₀‐I_h gives the (fullereno‐porphyrinato)zinc 6 still having three sulfolene units and a `diagonal' (difullerenoporphyrinato)zinc 7 that still has two sulfolene units, in 14 and in 43% yield, respectively.