Kinetic compensation effect and thermolysis mechanisms of organic polynitroso and polynitro compounds

The present study starts from the published values of the Arrhenius parameters E_a and log A of thermolysis in the condensed state of seven nitrosamines and one hundred organic polynitro compounds. On the basis of the linear relationship between E_aand log A, the set studied has been divided into several reaction series, each of which is characterized by a mechanism of primary thermolysis. For compounds with intense intermolecular interactions in a crystal, the classification mentioned is codetermined by the stabilizing effect of the crystal lattice. In the context of this effect, the absence of an effect of solid-liquid transition on thermal reactivity of octogen (HMX) has been confirmed. The idea also presented is that, in the primary homolysis in thermolyses of polynitro compounds, there takes place a mutual interaction of molecules of the given compound, which is analogous to termination interactions of nitroarenes in radical polymerizations.     

Benzoxazines and related compounds

The reaction of 2-mercapto(and benzylthio)-α,α-dialkylbenzyl alcohols with nitriles under the influence of acids serves as a method for the synthesis of 2,4,4-trisubstituted 4H-1,3-benzothiazines.     

Hydroacridines and related compounds

2-Phenyl-7,7-dimethyl-5H-7,8-dihydropyrano[4,3-b]pyridine and its N-oxide were synthesized. Refluxing of the latter with acetic anhydride gives 2-phenyl-7,7-dimethyl-8-hydroxy-5H-7,8-dihydropyrano[4,3-b]pyridine acetate; hydrolysis of the acetate gives the alcohol.See [1] for communication XII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 824–825, June, 1973.     

Hydroacridines and related compounds

The effect of substituents in the 9 and 10 positions on the reductive capacities of 9,10-disubstituted decahydroacridines was established in the case of the reduction of organic dyes (Methylene Blue, Indigo Carmine, and Brilliant Green).See [1] for communication XV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 969–972, July, 1977.     

Benzoxazines and related compounds

The action of a nitrating mixture on 2-substituted 4,4-diethyl-4H-1,3-benzoxazines gives the corresponding 6-nitro derivatives, which can be isolated as such or as the hydrolysis products –N-acyl-,-diethyl-2-hydroxy-5-nitrobenzylamines. The latter cyclize to the corresponding 4H-1,3-benzoxazines under the influence of perchloric acid.See [1] for communication III.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 303–305, March, 1972.     

Benzoxazines and related compounds

A simple method has been elaborated for synthesizing 2-substituted 4,4-dialkyl-4H-1, 3-benzoxazines by the interaction between nitriles and o-oxyphenyldialkylcarbinols under the influence of acids.For part I, [1].     

Hydroacridines and related compounds

3,3-Dimethyl-2-oxa-1,2,3,4-tetrahydroacridine and its N-oxide and 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydroacridine N-oxide were synthesized. On heating with acetic anhydride, the N-oxides form, respectively, acetates of 3,3-dimethyl-2-oxa-1,2,3,4-tetrahydro-4-acridinol and 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydro-4-acridinol. Hydrolysis of the acetates gives the alcohols themselves. Oxidation of 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydro-4-acridinol acetate gives the corresponding N-oxide. Oxidation of 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydro-4-acridinol with manganese dioxide gives 3,3,6,6-tetramethyl-2,7-dioxa-sym-octahydro-4-acridinone.See [9] for communication VII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1218–1221, September, 1971.     

Hydroacridines and related compounds

The N-oxides of 2,4-diphenyl-5,6,7,8-tetrahydroquinoline, 2,4-diphenylpyrindane, and 7,7-dimethyl-2,4-diphenyl-6-oxa-5,6,7,8-tetrahydroquinoline were synthesized. On heating with acetic anhydride, the N-oxides form, respectively, acetates of 2,4-diphenyl-5,6,7,8-tetrahydro-8-quinolinol, 2,4-diphenyl-7-pyrindanol, and 7,7-dimethyl-2,4-diphenyl-6-oxa-5,6,7,8-tetrahydro-8-quinolinol; hydrolysis of the acetates gives the alcohols.See [10] for communication X.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1547–1551, November, 1972.     

Hydroacridines and related compounds

4-Benzoylhydroacridines were synthesized by the reaction of 4-lithiohydroacridines with benzonitrile or benzoyl chloride. Their capacity for keto-enol tautomerism was noted.See [1] for communication IX.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 7, pp. 984–986, July, 1972.     

Hydroacridines and related compounds

One hydrogen atom is replaced by lithium in the reaction of 1,2,3,4-tetrahydroacridine and sym-octahydroacridine with phenyllithium; effective replacement of a second hydrogen atom by lithium becomes possible after replacement of the first lithium by an alkyl group. This makes it possible to achieve step-wise alkylation.See [1] for communication VIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 673–675, May, 1972.     

Gibberellins and related compounds

Conclusions A study was made of the photochemical aromatization of the 2-keto derivative of gibberellic acid in various solvents. Unusual fragmentation of the B ring, with the formation of the seco-structure, was observed when the reaction was run in benzyl alcohol.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2037–2040, September, 1971.     

Hydroacridines and related compounds

The stereochemistry of the hydride reduction of N-substituted 4a-cyano-, 4a,10a-dicyano-, and 4a,10a-peroxy-9-phenylperhydroacridines was studied. The configuration of a series of isomeric N-substituted 9-phenylperhydroacridines was established.See [1] for communication XIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 508–512, April, 1977.