Synthesis and transformations of polyhedral compounds 12. Stevens rearrangement in the azaadamantane series

Some quaternary salts of 1,3-diaza- and 1,3,5-triazaadamantanes undergo the Stevens rearrangement to give derivatives of the corresponding 1,4-diaza- and 1,3,6-triazahomoadamantanes. The structures of the rearrangement products were proved by IR, PMR, and mass spectroscopy and x-ray diffraction analysis (XDA).See [1] for Communication 11.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 669–673, May, 1991.     

Synthesis and transformations of polyhedral compounds. 16. Synthesis and some reactions of 7-aroyl- and 7-heteroyl-1,3,5-triazaadamantanes

7-Aroyl- and 7-heteroyl-1,3,5-triazaadamantanes were obtained by condensation of aromatic and heterocyclic compounds containing an acetyl group with hexamethylenetetramine in the presence of acetic acid. Reactions with 7-benzoyl- and 7-(4-nitrobenzoyl)-1,3,5-triazaadamantanes at both the carbonyl group and in the triazaadamantane ring were carried out. Ring-deuterated 7-nitro- and 7-(4-nitrobenzoyl)-1,3,5-triazaadamantanes were synthesized in order to ascertain the pathway of mass-spectrometric fragmentation, as well as a possible mechanism for the construction of the triazaadamantane ring.For Communication 15 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1565–1571, November, 1992.     

Synthesis and transformations of polyhedral compounds. Synthesis of 2-[quinolin-3(2)-yl]-1,3-diazaadamantanes

A number of new 1,3-diazaadamantane derivatives containing quinoline fragments on C² have been synthesized by condensation of 1,5-dialkyl-3,7-diazabicyclo[3.3.1]nonan-9-one, 1,5-dimethyl-3,7-diazabicyclo-[3.3.1]nonan-9-ol, and 1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonane with 2-oxo-1,2-dihydroquinoline-3-carbaldehyde, 2-chloro- and 2-iodoquinoline-3-carbaldehyde, and quinoline-2-carbaldehyde.     

Synthesis and transformations of polyhedral compounds. 14. Opening of hexahydropyrimidine ring of 2-substituted 1,3-diazaadamantanes by electrophilic reagents

It was found that a cleavage of the N-C bonds of C-mono- and C,C-disubstituted methylenediammo groups of 1,3-diazaadamantanes takes place by the action of electrophilic reagents.For Communication 13, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 929–932, July, 1992.     

Synthesis and conversions of polyhedral compounds 18. Conversion of 1,3-diaza- and 1,3,5-triaza-adamantanes into new nitrogen-containing polyhedral compounds under the influence of dibasic acid dichlorides

Derivatives of 1,3-diaza- and 1,3,5-triazaadamantanes react with dicarboxylic acid dichlorides, forming derivatives of new heteropolyhedral compounds containing a dicarboxylic acid residue in place of CH₂ or CRR¹ of the methylidenamino fragment of the azaadamantanes.Translated from Khimiva Geterotsiklicheskikh Soedinenii, No. 3, pp. 393–396, March, 1994.     

Synthesis and conversions of polyhedral compounds 17. Conversion of 1,3-diaza- and 1,3,5-triazaadamantanes to nitrogen-containing pentacyclic compounds

It has been shown that derivatives of 1,3-diaza- and 1,3,5-triazzaadaniantanes, and also derivatives of 3,7-diazabicyclo[3.3.1]nonane, interact with 3,7-bis(bromoacetyl)-3,7-diaza- and 3,7-bis(bronwacetyl)-1,3,7-triazabicyclo[3. 3. 1]nonanes in the presence of bases to form previously unknown types of heteropolyhedral structures — nitrogen-containing pentacyclic compounds.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 106–110, January, 1994. Original article submitted October 20, 1993.     

Synthesis and conversions of polyhedral compounds 20. Synthesis of certain derivatives of 3,7-diazabycyclo[3.3.1]nonane

1,3-Diazaadamantanes containing hydrogen atoms or a hydroxyl or oxime group at C₍₆₎, under the action of 2 moles of aralkyl halides, are converted in alkaline aqueous media to 3,7-diaralkyl-3, 7-diazabi cyclo(3.3.1]nonanes containing the indicated groups at C₍₉₎. Analogously, quaternary salts of 1,3-diaza-adamantanes containing hydrogen atoms or a hydroxyl group at C₍₆₎ are converted in an alkaline aqueous medium to the corresponding 3-alkyl-3,7-diazabicyclo[3.3.1]nonanes containing the indicated groups at C₍₉₎.For Communication 19, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 401–406, March, 1994.     

Conjugates of polyhedral boron compounds with carbohydrates

Conjugates of β-lactosylamine derivatives bearing terminal amino groups in aglycon with ortho-carboranylacetic acid were synthesized. Five glycoconjugates with spacers of different length (from 9 to 18 atoms) and hydrophilicity containing di-, tri-, and pentapeptide fragments constructed of glycine and serine residues and spacers incorporating ethylenediamine and tartaric acid or tertiary amine residues were prepared Dedicated to the memory of outstanding chemist and biochemist V. N. Shibaev. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2033–2036, October, 2007.     

Synthesis of new iminocoumarins and their transformations into N-chloro and hydrazono compounds

The Knoevenagel reaction between 2-hydroxybenzaldehydes and active methylene compounds (malononitrile and ethyl cyanoacetate) produces iminocoumarins and/or coumarins. In order to study the reactivity of the prepared iminocoumarins, chlorination and reaction with N-nucleophiles were studied.     

Synthesis and conversions of polyhedral compounds 19. Opening of ring of 1,3,6-triazohomoadamantane by electrophilic reagents

A new method has been developed for obtaining 8-nitro-1,3,6-triazahomoadamantane. By the action of electrophilic reagents on this compound, N-C bonds of the methylenediamino fragment are ruptured, forming derivatives of 1,4,8-triazabicyclo[4.3.1]decane. Depending on the conditions in reactions of 8-nitro-1,3,6-triazohomoadamantane with benzoyl chloride and nitrous acid, derivatives of either 1,4,8-triazabicyclo[4.3.1]decane or hexahydro-1,4-diazepine may be obtained. The formation of the latter proceeds through the above-mentioned derivatives of 1,4,8-triazabicyclo[4.3.1]decane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 397–400, March, 1994.     

Thermolytic transformations of polyfluoroorganic compounds

Copyrolysis of 4-chlorotetrafluorobenzotrichloride with chlorodifluoromethane (as the source of difluorocarbene) gave 4-chlorodifluoromethyl--chlorohexafluorostyrene, 1,4-dichlorotetrafluorobenzene, and 4-(chlorodifluoromethyl)chlorotetrafluorobenzene along with 4-chloro--chlorohexafluorostyrene. Possible routes for the formation of these products have been offered.For Part 30, see Ref. 1.Translated fromIzevstiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2199–2202, December, 1994.     

Thermolytic transformations of polyfluoroorganic compounds

The reaction of α,α-dichlorooctafluoroethylbenzene with tetrafluoroethylene as a source of difluorocarbene has been studied. The copyrolysis of these compounds gave not only the expected products, decafluoro-α-methylstyrene and α-chloroheptafluorostyrene, but also noticeable amounts of perfluoro-1-methylindan and perfluoro-7-methylbicyclo[4.3.0]nona-1,4,6-triene along with perfluoro-3-methylindene and octafluorostyrene. It has been suggested that indan and the triene are formed with the participation of the C₆F₅CCICF₃ radical through sigmatropic shifts of fluorine atoms in the intermediate bicyclic compounds. The reaction of α,α-dichlorodecafluoropropylbenzene with tetrafluoroethylene afforded α-chloroheptafluorostyrene as the main product.     

Synthesis and application of polyhedral oligosilsesquioxanes and spherosilicates

Data on methods for the synthesis of reactive polyhedral oligomeric silsesquioxanes and spherosilicates are summarized and their influence on the properties of polymer systems is considered. It has been shown that these compounds hold promise for electronics, optics, aerospace technology, and medicine.     

Synthesis of novel starburst and dendritic polyhedral oligosilsesquioxanes

The hydrosilylative reaction utilizing octakis(dimethylsiloxy)silsesquioxane and silsesquioxane disilanols bearing alkenylsilyl moieties produces a series of starburst-type giant silsesquioxanes and a second-generation dendritic molecule as well as a boron-containing one.     

Synthesis and transformations of metallacycles

The Cp₂ZrCl₂-catalyzed reaction of arylolefins (styrene,o- andp-methylstyrenes,trans-stilbene, 1,4-diphenyl-1,3-butadiene) with AlEt₃ resulting in mono- and disubstituted alumacyclopentanes and substituted alumacyclopropanes was studied. The yield and ratio of cyclic organoaluminum compounds depend on the structure of the initial arylolefins and conditions of cycloalumination.