Mass spectrometry of the 11H-dibenzo[c,f][1,2]-diazepine system

The mass spectra of 3,8-dichloro-11H-dibenzo[c,f] [1,2]diazepine, the corresponding diazepin-11-01 and diazepin-11-one and their dihydro and N-oxide derivatives have been recorded. The most important fragmentation of the molecular ions of all diazepines studied was an initial loss of m/e 28, with further fragmentation depending on the 11-substituent. No general pathway was observed for the corresponding N-oxides and dihydro compounds.     

Paramagnetic ring currents in the carbanion of 5H-dibenzo [a,d] cycloheptene and the nitranion of 5H-dibenz[b,f] azepine

The proton NMR spectra of the carbanion of 5H-dibenzo[a, d] cycloheptene (DbcH^?) and the nitranion of 5H-dibenz[b, f] azepine (Dba?) have been recorded and interpreted. Numerical values for the ring current in each ring have been estimated by a least squares analysis of the observed chemical shifts, after applying corrections for the excess charges and local electric dipoles. The results point to a strong paramagnetic ring current in the seven-membered ring, the one in DbcH? being larger than in Dba?.     

Eight-membered heterocycles. 12H-dibenzo[d,g][1,3,2]dioxaphosphocin and 12H-dibenzo[d,g][1,3,2]dioxaborocin derivatives

The synthesis of phosphonite and thiophosphite derivatives of the 12H-dibenzo[d,g][1,3,2]dioxaphosphocin ring system is described. The 'H nmr shows evidence for long-range coupling of the C-12 methine proton to phosphorus. The ¹H nmr of the 12H-dibenzo[d,g][1,3,2]dioxaborocin ring system is compared to that of the phosphorus analog. The nmr spectral data suggest that the phosphorus and boron containing ring systems have similar ring conformations.     

2-羟基-1O,11-二氢-5H-二苯并[a,d]环庚烯-5-酮的合成

以2－羟基苯甲醛和3－甲氧基苯乙酸为原料,经3步反应合成2－羟基－10,11－二氢－5H－二苯并[a,d]环庚烯－5－酮。     

11-Amino-5H-dibenzo[b,e]-1, 4-diazepine. 10. Mitteilung über siebengliedrige Heterocyclen

11-Amino-5H-dibenzo[b,e]-1, 4-diazepines V, several of which possess neuroleptic properties, have been prepared using three methods:

• 1 Aminolysis of either iminothioethers IV (X = methyl or an activating group such as cyanomethyl and p-nitrobenzyl) or the iminochlorides III.
• 2 Bischler-Napieralski type cyclodehydration of o-anilinophenyl-ureas IX (only applicable for the synthesis of compounds V where R is other than hydrogen).
• 3 Cyclodehydration of amino-amides VII by various condensing agents.

     

He I photoelectron spectra and gas-phase electronic structures of end-functionalized [3]- and [5]-ladderanes

[3]- and [5]-ladderanes obtained by way of template-controlled syntheses conducted in the organic solid state have been characterized via He I photoelectron (PE) spectroscopy. The results provide a first correlation with X-ray crystallographic structure data and establish the reliability of quantum chemical DFT (B3LYP/6-31G*) and ab initio HF calculations in predicting geometrical and electronic structures of molecular ladder frameworks.     

Conformation and internal mobility of 5H-dibenzo[a,d]cycloheptene derivatives in solution. Conformational analysis of highly flexible structures,part II

Summary The conformational possibilities of 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cycloheptene (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (2), and 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cycloheptene (3) are analysed using empirical force field methods. Minimum energy conformations, interconversion pathways, interconversion graphs and interconversion energies are examined in view of the analysis of conformer equilibria of1,2, or3 in solution. In addition, some basic requirements of the analysis of fast interconverting conformers using the lanthanide induced shift method are discussed.

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Konformation und interne Beweglichkeit von 5H-Dibenzo[a,d]cyclohepten Derivaten in Lösung. Konformationsanalyse hochflexibler Strukturen, Teil 2

Zusammenfassung Die konformativen Möglichkeiten von 5-(3-N,N-dimethylaminopropyl)-5H-dibenzo[a,d]cyclohepten (1), 5-(3-N,N-dimethylaminopropylidene)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (2) und 5-(3-N,N-dimethylaminopropyl)-10,11-dihydro-5H-dibenzo[a,d]cyclohepten (3) wurden mit Hilfe empirischer Kraftfeldmethoden analysiert. Jene Konformationen, die einem energetischen Minimum entsprechen, sowie Interkonversionswege, Interkonversionsgraphen und Interkonversionsenergien wurden in Hinblick auf die Analyse der Konformerengleichgewichte von1,2 oder3 in Lösung untersucht. Weiters werden noch einige grundlegende Voraussetzungen für die Analyse von sich schnell ineinander umwandelnden Konformeren mittels der Lanthaniden-induzierten Verschiebungsmethode besprochen.

     

On the chemistry of pyridazines,XXXVI: Novel diaza-analogs of 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-one

Procedures for the preparation of the novel tricyclic ketones 10,11-dihydro-5H-benzo[4,5]cyclohepta[1,2—d]pyridazin-5-one (3), 5,6-dihydro-11H-benzo[4,5]cyclohepta[2,1—c]pyridazin-11-one (4), and 10,11-dihydro-5H-benzo[4,5]-cyclohepta[1,2—c]pyridazin-5-one (5) starting from a preformed 1,2-diazine system are proposed. The key intermediates7,19, and11 are prepared from (2-phenylethyl)pyridazines6 and18 by introduction of a carboxylic functionality via homolytic alkoxycarbonylation or via a sulfonylReissert-type reaction.

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Zur Chemie von Pyridazinen, 36. Mitt.: Neuartige Diazaanaloga des 10,11-dihydro-5H-dibenzo[a,d]cyclohepten-5-ons

Zusammenfassung Methoden zur Darstellung der neuen trizyklischen Ketone 10,11-Dihydro-5H-benzo[4,5]cyclohepta[1,2—d]pyridazine-5-on (3), 5,6-Dihydro-11H-benzo[4,5]cyclohepta[2,1—c]pyridazin-11-on (4) und 10,11-Dihydro-5H-benzo[4,5]cyclohepta[1,2—c]pyridazin-5-on (5) ausgehend von einem präformierten 1,2-Diazinsystem werden vorgeschlagen. Die Schlüsselbausteine dieser Synthesen7,19 und11 werden durch Einführung einer Carboxylfunktion in die (2-Phenylethyl)pyridazine6 und18 über homolytische Alkoxycarbonylierung bzw. eine Sulfonyl-Reissert-Reaktion erhalten.

     

Derivatives of 10,11-dihydro-5H-dibenzo[a,d] cycloheptene and related compounds. III. Azaketones

The preparation and properties of four isomeric azadibenzoeycloheptenones 3 and their 10,11-dihydro derivatives 2 are described. The ketones 2 were prepared by cyclization of appropriately substituted phenethylpyridine carboxylic acids and dehydrogenated to 3 . Four monochloro derivatives 24 of the 4-azaketone 2d are also described.