The structure of 2,4,6-tris[di(tert-butoxycarbonyl)methylidene]-hexahydro-1,3,5-triazine

The structure of 2,4,6-tris[di(tert-butoxycarbonyl)methylidene]hexahydro-1,3,5-triazine was studied by quantum chemistry, NMR and IR spectroscopy, and X-ray diffraction. This compound exists exclusively in the hexahydro-1,3,5-triazine form both in solution and in the solid phase, although due to the loss of the aromatization energy, this structure should be less stable than a 1,3,5-triazine structure. The formation of strong intramolecular hydrogen bonds confirmed by NMR and IR spectroscopy and X-ray diffraction data may be a main reason for stabilization of the hexahydro-1,3,5-triazine isomer. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1022–1026, June, 2006.     

Synthesis of substituted 2-amino-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazines

A procedure was developed for the synthesis of substituted 2-amino-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazines from 2-chloro-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazine and aliphatic and aromatic amines. The data of¹⁹F NMR spectroscopy are indicative of the presence of a barrier to internal rotation. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1568–1572, August, 1999.     

Synthesis and structures of 4,6-disubstituted 2-(5-methyl-1,2,4-oxadiazol-3-yl)-1,3,5-triazines

New 1,2,4-oxadiazolyl-1,3,5-triazines were synthesized from amidoximes derived from sym-triazine mononitriles. The structure of one of the resulting compounds was studied in detail by X-ray diffraction. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1845–1850, August, 2005.     

Local dipole interactions induce helicity of (<Emphasis Type="Italic">S</Emphasis>)-2-butyl-<Emphasis Type="Italic">N</Emphasis>-(1,8-naphthaloyl)-2-aminobenzoate molecules containing 1,8-naphthalimide rings utilized as a column building blocks: X-ray and quantum mechanical studies

In the crystal of triclinic symmetry the title compound contains four independent molecules, which differ in the conformation of the aliphatic carbon chain (T, G ⁺and G ⁻) and in the helicity (M or P) of the N-(1,8-naphthaloyl)-2-aminobenzoate (NAB) unit. Quantum chemical MP2 calculations showed that isolated molecules favor helicity of NAB bichromophores most likely due to attractive interactions between local dipoles formed along carbonyl bonds, such that the helical arrangement of O=C–C–C–N–C=O fragments is stabilized by intramolecular interactions between terminal anti-parallel local carbonyl dipoles. In the crystal structure, columnar stacking of the anti-parallel 1,8-naphalimide rings is observed. In a column the neighboring NAB units display opposite helicity.     

Synthesis of 1,3-diazapyrenes from benzo[<Emphasis Type="Italic">f</Emphasis>]quinazolines

Methods have been developed for the synthesis of 1,3-diazapyrenes based on the reactions of 1-methylbenzo[f]quinazolines with DMF dimethyl acetal or with 1,3,5-triazine in PPA. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii. No. 2, pp. 260–262, February, 2009.     

The solid-state interaction of organometallic aldehydes with 1,8-naphthylenediamine

Organometallic derivatives of 2,3-dihydroperimidine were obtained by the solid state interaction of ferrocene-, cymantrene-, and ruthenocenecarbaldehydes with 1,8-naphthylenediamine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 1, pp. 145–146, January, 2000.     

The solid-state interaction of organometallic aldehydes with 1,8-naphthylenediamine

Organometallic derivatives of 2,3-dihydroperimidine were obtained by the solid state interaction of ferrocene-, cymantrene-, and ruthenocenecarbaldehydes with 1,8-naphthylenediamine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 1, pp. 145–146, January, 2000.     

peri-naphthylenediamines

First indirect evidence for the formation of a radical cation of 1,8-bis(dimethylamino)naphthalene (“proton sponge”) in reactions with HNO₃, HNO₂, NO₂, and I₂ has been obtained. In all cases, the products of reaction of the radical cation with nucleophiles and/or its dimer, 4,5,4′,5′-tetrakis(dimethylamino)-1,1′-binaphthyl, have been isolated. 4-Chloro-1,8-bis(dimethylamino)naphthalene has been regioselectively synthesized in high yield. For Part 24, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 320–324, February, 1998.     

A novel 1,8-naphthalimide probe: synthesis and interactions with nucleic acid and its precursor

Three novel, water-soluble N-substituted 1,8-naphthalimides as the spectroscopic probes of nucleic acid, N-(2-hydroxyethyl)-1,8-naphthalimide (NI1), 1,8-naphthalimide-N-acetic acid (NI2) and 1,8-naphthalimide-N-caproic acid (NI3), were synthesized and photophysically characterized. The steady-state fluorescence quenching of the NI probes with nucleic acids (NA) and their precursors (nucleobases and nucleosides) were studied by Stern–Volmer correlation. The rate constants for bimolecular quenching were obtained in Tris buffer solution. The transient absorption spectroscopy by nanosecond laser flash photolysis were explored to identify the transient species and to determine the kinetics. The dynamic interaction mechanism was attributed to electron transfer (ET) and energy transfer via ³NI.     

Trisubstituted 1,3,5-triazines. 2. Synthesis of 1,3,5-triazines from 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine

A study was carried out on electrophilic addition and hydrolytic dissociation of 2,4,6-tris[di(tert-butoxycarbonyl)methylene]hexahydro-1,3,5-triazine. Chloro, bromo, and methyl derivatives of tris[di(tert-butoxycarbonyl)methyl]-1,3,5-triazine were synthesized for the first time as well as 2,4,6-tris-(tert-butoxycarbonylmethyl)-1,3,5-triazine. For Communication 1, see ref. [1]. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow and Institute of Chemical Physics, Russian Academy of Sciences at Chernogolovka, 142432 Chernogolovka, Moscow Oblast. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1404–1407, October, 1998.     

Photo-stability of yellow-green emitting 1,8-naphthalimides containing built-in s-triazine UV absorber and HALS fragments and their acrylonitrile copolymers

Two novel 1,8-naphthalimide dyes, containing active fragments of both 2-(2-hydroxyphenyl)-1,3,5-triazine UV absorber and 2,2,6,6-tetramethylpiperidine radical scavenger as well as a polymerisable allyl group, were designed as multifunctional yellow-green emitting fluorophores capable simultaneously of chemically fluorescent dyeing and photo-stabilisation of polymers. Their basic photo-physical characteristics have been determined and are discussed. It was shown that combination of different structural units in the 1,8-naphthalimide molecule does not result in their interaction through intramolecular fluorescence quenching due to an electronic energy transfer. The ability of the combined dyes to copolymerise with acrylonitrile was demonstrated as polyacrylonitriles stable to solvents and with an intense colour and fluorescence were obtained. Photo-degradation of the new fluorophores and their influence on the photo-stability of the coloured copolymers have been studied and compared to other similar fluorescent dyes, not containing either UV absorber or hindered amine fragment in their molecules as well as not containing both of them. Novel fluorophores showed the best photo-stability in both solution and polymer. A significant photo-stabilising effect towards photo-destruction of polyacrylonitrile was found, which might be caused by a possible “synergism” of two stabiliser fragments differing in their action.     

Superacidic cyclization of ω-hydroxygeraniol diacetate and ω-hydroxygeraniol benzyl ether acetate

Low-temperature superacidic cyclization of (E,E)-3,7-dimethylocta-2,6-diene-1,8-diol (ω-hydroxygeraniol) diacetate and (E,E)-8-acetoxy-1-benzyloxy-3,7-dimethylocta-2,6-diene leads to the same mixtures of two diastereomeric 9-acetoxy-8-hydroxy-p-menth-1-enes epimeric at the C(8) atom. Translated fromIzvestiya Akademii Nauk Seriya Khimicheskaya, No. 1, pp. 135–138, January, 1999.     

Influence of steric and electronic effects of substituents on the molecular structures and conformational flexibility of 1,8-naphthalenedicarboximides

A series of 1,8-naphthalenedicarboximide derivatives containing substituents of different steric and electronic nature were studied by X-ray diffraction analysis.Ab initio quantumchemical calculations in the HF/3–21G approximation demonstrated the high conformational flexibility of the imide tetrahydro ring in the molecules of these compounds. The electronic nature of the substituents has no effect on the geometry and conformational flexibility of naphthalenedicarboximides due to weak conjugation between the imide and naphthalene fragments in the molecules. However, the steric effects of the bulky substituents noticeably affect the equilibrium geometry of the imide ring by increasing its conformational flexibility. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 68–73, January, 2000.     

Influence of steric and electronic effects of substituents on the molecular structures and conformational flexibility of 1,8-naphthalenedicarboximides

A series of 1,8-naphthalenedicarboximide derivatives containing substituents of different steric and electronic nature were studied by X-ray diffraction analysis.Ab initio quantumchemical calculations in the HF/3–21G approximation demonstrated the high conformational flexibility of the imide tetrahydro ring in the molecules of these compounds. The electronic nature of the substituents has no effect on the geometry and conformational flexibility of naphthalenedicarboximides due to weak conjugation between the imide and naphthalene fragments in the molecules. However, the steric effects of the bulky substituents noticeably affect the equilibrium geometry of the imide ring by increasing its conformational flexibility. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 68–73, January, 2000.     

Cyanamides in cyclization reactions with anthranilates, 2-aminophenyl ketones, and methyl 2-(3-oxopiperazin-2-yl)acetate

Cyclization of aryl-, aroyl-, and (4,6-dimethylpyrimidin-2-yl)cyanamides with methyl anthranilates, 2-aminophenyl ketones, and methyl 2-(3-oxopiperazin-2-yl)acetate leads to 2-amino-3,4-dihydroquinazolin-4-one, 2-aminoquinazoline, and 6-amino-1,3,4,8,9,9a-hexahydro-2H-pyrazino[1,2-c]pyrimidine-1,8-dione derivatives, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 164–170, January, 2008.     

Transformations of sym-octahydroxanthene-1,8-diones and 1,8-dioxo-sym-octahydroxanthylium salts in recyclization under the influence of amines

The chemical behavior of 9-R-sym-octahydroxanthene-1,8-diones and salts based on them in recyclization reactions under the influence of amines was studied. The effect of the basicity of the amines on the direction of recyclization was established. A method is proposed for the single-stage synthesis of sym-octahydroacridine-1.8-dione oximes based on 1,8-dioxo-sym-octahydroxanthenes. Conditions were worked out for the oxidation of sym-octahydroxanthene-1,8-diones and N-R-decahydroacridinediones to the corresponding salts. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 32–38, January, 2006.     

Synthesis of 1,3,7-triazapyrene and 1,2,3,7-tetraazapyrene derivatives as a result of anomalous Hoesch reaction

Method for the synthesis of 6,8-diaryl-1,3,7-triazapyrenes and 6,8-diaryl-1,2,3,7-tetraazapyrenes, based on the reaction of 2-R-1H-perimidines and 1H-naphtho[1,8-de][1,2,3]triazine with aromatic nitriles in polyphosphoric acid, has been elaborated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 209–210, January, 2008.     

Amine exchange reactions of 3-<Emphasis Type="Italic">tert</Emphasis>-butyl-6-(methylsulfanyl)-1,2,3,4-tetrahydro-1,3,5-triazine hydroiodide with amino acids

3-tert-Butyl-6-(methylsulfanyl)-1,2,3,4-tetrahydro-1,3,5-triazine hydroiodide enters into the amine exchange reaction with glycine and β-alanine in aqueous solution. The final exchange products are [4-(methylsulfanyl)-5,6-dihydro-1,3,5-triazin-3-ium-1(2H)-yl] acetate and 3-[4-(methylsulfanyl)-5, 6-dihydro-1,3,5-triazin-3-ium-1(2H)-yl] propanoate, respectively, crystallizing together with t-butylamine hydroiodide from aqueous or aqueous alcoholic solutions as ion associates, which also can be detected in solution in DMSO-d ₆. [4-(Methylsulfanyl)-5,6-dihydro-1,3,5-triazin-3-ium-1(2H)-yl] acetate can be extracted directly from the reaction mixture after carrying out the amine exchange in aqueous isopropanol or 95% ethanol, as well as by “recrystallization“ of its associate with tert-butylamine hydroiodide from aqueous isopropanol.     

Use of the ring opening reactions of 1,3,5-triazines in organic synthesis (review)

Published data on the recyclization reactions of 1,3,5-triazines are reviewed. The classification is based on the fragments of the 1,3,5-triazine molecules used in the construction of new heterocycles. Dedicated to the birthday of A. F. Pozharskii, who has made a great contribution to our establishment as scientists. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 167–190, February, 2009.     

Synthesis of N-trinitroethyl derivatives of linear and heterocyclic nitrogen-containing compounds

Earlier unknown N-trinitroethyl derivatives of acetylhydrazine, 4-amino-1,2,4-triazole, and 2,4,6-triamino-1,3,5-triazine, which are potential components for gas-generating formulations, were synthesized. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1306–1309, May, 2005.