Propellanes. Part LXXX. Baeyer-Villiger Oxidation of [4.3.3]Propellane-8,11-dione

Oxidation of the title compound with m-chloroperbenzoic acid affords a keto-lactone, two bis-lactones and a bis-spirolactone, in varying amounts depending upon the reaction conditions. The structures were established by means of X-ray diffraction, ¹H- and ¹³C-NMR spectroscopy.     

Propellanes : XCVIII. Treading of anti,anti[20.3.3]propellane-24,27-diol by sebacic acid

A spherical cyclic diester has been prepared from the title components, separated from by-products, and purified by aid of double labelling of the components with ³H and ¹⁴C, respectively. The product may be viewed as a doubly-anchored rotaxane.     

Propellanes. Part LXXVIII. Preparation of Several Triaza[3.3.3]propellanes and an Oxadiaza[3.3.3]propellane

3,7,10-Tribenzyl-3,7,10-triaza[3.3.3]propellane ( 4a ), 3,7-dibenzyl-10-phenyl-3,7,10-triaza[3.3.3]propellane ( 4c ), 3,7-dibenzyl-10-(p-tolyl)-3,7,10-triaza[3.3.3]propellane ( 4b ), and 3-oxa-7,10-diaza[3.3.3]propellane ( 6 ) have been prepared.     

Propellanes. Part LXIX. Preparation of lactones from the three isomeric [4.3.3]propellane-8,11-diols

Each of the three isomeric[4.3.3]propellane-8,11-diols was lactonized by using 1, ω-diacids of different chain lengths. The minimal chain length required to bridge the syn-syn diol is –CO(CH₂)₁₁CO–.     

Propellanes. LXVII. Reactions of 1, 6-bridged [10]annulenes with 4-methyl-1,2,4-triazoline-3, 5-dione

Reactions of 11-substituted-1, 6-methano [10]annulenes and 1, 6-methano [10]-annulenes substituted in the aromatic ring with the title dienophile are described.     

Propellanes. LXII. The endo- and exo-adducts of 11-cyano-1,6-methano[10] annulene with 4-methyl-1,2,4-triazoline-3,5-dione

The title compounds have been isolated and their structures determined by X-ray crystallography. Their relative stability is discussed in terms of theory and experiment. The endo-adduct is the thermodynamically more stable one.     

Propellanes—XXXI : The diels-alder reaction of [4.4.2]propellanes with 4-phenyl-1,2,4-triazoline-3,5-dione

Attack of a number of [4.4.2]propellanes by the dienophile named in the title occurs, when one equivalent of dienophile is used, for the direction anti- to the 4-membered ring.     

Heterocyclic quinones with bridgehead nitrogen atoms. Part I. Pyrrolo[1,2-a]quinoxaline-6,9-dione and pyrrolo[2,1-c][1,2,4]benzotriazine-6,9-dione

The synthesis and some reactions of pyrrolo[1,2-a]quinoxaline-6,9-dione and pyrrolo[2,1-c][1,2,4]benzotriazine-6,9-dione are described.     

[3.3.2]- and [3.3.3]Propellanes in Reactions with Oxidizing Electrophiles

The structure of [3.3.2]- and [3.3.3]propellanes, their framework analogs, and their radical-cations was investigated by computational methods (BLYP and B3LYP) in the 6-31G* basis set. The reactivity of the propellanes toward model oxidizing electrophiles does not contradict the quantum-chemical calculations. In the case of the tetracyclic framework analog of [3.3.3]propellane the reaction takes place as C—H substitution, whereas in the case of [3.3.2]propellanes it takes place as C—C-oxidative addition.     

The Synthesis of Some Bifunctionally Substituted [3,3,1] Propellanes

Convenient syntheses of some bifunctionally substituted [3.3.1] propellanes are reported from the readily accessible tricyclo[4.3.1^1,6] dec-3-en-8-ol.     

Propellanes—XLIV: Reaction of 11-substituted-1,6-methano[10]annulenes with 4-phenyl-1,2,4-triazoline-3,5-dione

Reaction of the bridged annulene derivatives and the dienophile mentioned in the title occurs through attack by the latter from below, anti- to the bridge. The mono-adducts obtained contain a substituted cyclopropane ring. Attempted nucleophilic displacement of suitable substituents was unsuccessful.     

Propellanes. Part LXXI. Confirmation of predicted regiospecificity in Diels-Alder reactions of certain propellanes with 4-phenyl-1,2,4-triazoline-3,5-dione

Two isomeric propellane epoxides 1a and 1b containing a cyclohexadiene ring are attacked by the title dienophile as predicted, syn to the five-membered ether ring whose α-hydrogens exert less repulsion than the α-epoxy hydrogens or the epoxide oxygen, respectively, of the cyclobutane ring.     

Naphthomoles. 7. Synthesis of 4,11-dimethoxynaphtho[2,3-f]indole-5,10-dione and 4-methoxynaphtho[2,3-f]-indole-5,10-dione

4,11-Dimethoxynaphtho[2,3-f]indole-5,10-dione and 4-methoxynaphtho[2,3-f[indole-5,10-dione have been synthesized by the Leimgruber-Batcho reaction from 1,4-dimethoxy-2-methyl-3-nitroanthraquinone.Russian University of Chemical Technology, Moscow 125190. Center for Drug Chemistry, All-Russian Scientific Research Institute for Pharmaceutical Chemistry, Moscow 119815. Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 8, pp. 1050–1054, August, 1996. Original article submitted March 20, 1996.     

Propellanes. Part LXXXI. Why are tetrakis[organoboranediylbis(oxy)]cyclobutanes formed without a trace of the isomeric tetrakis-dioxabora[3.3.2]propellanes?

MNDO and STO-3G calculations rationalize the relative instability of the title propellanes vis-à-vis the title products that are formed exclusively.