Theoretical design of blue emitting materials based on symmetric and asymmetric spirosilabifluorene derivatives

Equilibrium ground state geometry configurations and their relevant electronic properties of four experimentally reported asymmetric spirosilabifluorene derivatives are calculated by the HF(DFT)/6-31G(d) method. Their excited state geometries are investigated using the CIS/6-31G(d) method. The absorption and emission spectra are evaluated using the TD-B3LYP/6-31G(d) and TD-PBE0/6-31+G(d) levels both in gas phase and CHCl₃ solvent. Our results show an excellent agreement with the experimental data on their optical properties. To predict the substitution effect, the H/R (R = –NO₂, –CN, –NH₂ and –OCH₃) substituted symmetric and asymmetric spirosilabifluorene derivatives are also investigated, and the optical properties of H/R substituted derivatives are predicted in gas phase and CHCl₃ solvent. In comparison with the parent compound, significant red-shift is predicted for the emission spectra of the di-substituted symmetric derivatives with –NH₂ (96 nm), –OCH₃ (61 nm) and the push–pull (containing both –NH₂ and –NO₂) derivative (56 nm). It is found that the performance and the optical properties of these derivatives can be improved by adding push–pull substitutents. The largest change in the electronic and optical properties of this system can be obtained upon symmetric di-substitution among mono-, di-, tri- and tetra-substitutions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Etheno derivatives of adenine and cytosine (review)

The method of modification of heterocyclic bases of nucleic acids with chloroacetaldehyde and other α-halo carbonyl compounds is examined in this review. The mechanism, kinetics, and scope of the reaction, the chemical properties of modified derivatives of adenine and cytosine, and the possibilities of the application of etheno derivatives of adenine and cytosine in biochemistry and molecular biology are discussed. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 291–305, March, 1980.     

Mechanochemical synthesis and properties of fullerene derivatives

A technique was developed of mechanochemical synthesis of the fullerene C₆₀ water-soluble derivatives. The derivatives obtained were characterized by elemental analysis, IR spectroscopy, and thermogravimetric analysis. The effect the substances obtained on the mechanical properties of the polyvinyl alcohol films was studied. A strengthening effect of fullerene derivatives on the elastic modulus, tensile strength, and tensile deformation of the polyvinyl alcohol films were found to become apparent already at the concentrations of 0.1–0.2 wt %.     

Amino acid and peptide derivatives of fullerene

A general method for the synthesis of amino acid and peptide derivatives of fullerene (ADF) was developed, and the physicochemical properties of the compounds obtained were studied. ADF were shown to penetrate into liposomes and to exhibit adjuvant properties and antiviral activity. Deceased Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1050–1054, May, 1998.     

Aziridine and hydroxy- and chloroethylamine derivatives of colchicine and their biological activity

With the aim of enhancing the cytostatic properties of the initial alkaloid, new aziridine and bis(chloroethyl)amine derivatives of colchicine have been synthesized by the direct interaction of colchicine with chloroethylamine hydrochloride and also via the mono- and diethanolamine derivatives. The structures of the compounds obtained have been studied by spectral methods. An increased radiomodifying and antitumoral activity and a decreased toxicity of the substances synthesized as compared with the initial colchicine has been shown. Results obtained in the National Cancer Institute of the USA from the study of the cytostatic activity of the bis(chloroethyl)amino derivative of 60 tumor lines are presented. Institute of Oncology and Radiology, Academy of Sciences of the Republic of Uzbekistan. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 782–789, November–December, 1998.     

Oxidation by chlorine dioxide of methionine and cysteine derivatives to sulfoxides

Methionine and cysteine derivatives were oxidized asymmetrically by chlorine dioxide to sulfinyl derivatives. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 608–610, November–December, 2008.     

Ozonolysis of 11-desoxoglycyrrhetic acid and its derivatives

12-Oxo derivatives of 11-desoxolycyrrhetic acid and its derivatives were produced by oxidative transformation using ozone. Olean-3,12-dion-30-oic acid was produced for the first time by exhaustive ozonolysis of 11-desoxoglycyrrhetic acid at −60°C. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 469–472, September–October, 2007.     

Membrane-active properties and antiradical activity of gossypol and its derivatives

A novel asymmetric gossypol derivative was synthesized. The antioxidant activity of gossypol and certain of its derivatives at the aldehyde groups and the interaction of these compounds with model membranes were studied. It was shown that the antiradical and membrane activities of the gossypol derivatives were determined by the structure of the substituent and that gossypol and its derivatives were partially localized in the lipid bilayer and possibly induced formation of a new interdigitating phase. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 265–266, May–June, 2008.     

Thermooxidative degradation of watersoluble acetylcellulose and its carboxycontaining derivatives

The thermooxidative degradation of water-soluble acetylcellulose and some of its carboxy-containing derivatives has been studied by the methods of thermal analysis. A relationship has been established between the thermostability of the aceto-mixed derivatives and the nature of the substituting group. Tashkent Institute of Chemical Technology. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 703–705, September–October, 1998.     

Synthesis and properties of aminomethyloxy derivatives of (1-Propylsulfanyl)pentane

New 2-aminomethyloxy derivatives of 1-(propylsulfanyl)pentane were prepared by condensation of 1-(propylsulfanyl)pentan-2-ol with formaldehyde and secondary amines. The starting 1-(propylsulfanyl)pentan-2–ol was synthesized by the reaction of 1–propanethiol with 1–bromopentan–2–ol. The structures of the products were proved by elemental analysis, IR and ¹H NMR spectroscopy, and mass spectrometry. The compounds were tested as antimicrobial additives to lubricating oils and as antiseptics against bacteria and fungi.     

Use of Cartesian coordinates in evaluation of multicenter multielectron integrals over Slater type orbitals and their derivatives

Using addition theorems for interaction potentials and Slater type orbitals (STOs) obtained by the author, and the Cartesian expressions through the binomial coefficients for complex and real regular solid spherical harmonics (RSSH) and their derivatives presented in this study, the series expansion formulas for multicenter multielectron integrals of arbitrary Coulomb and Yukawa like central and noncentral interaction potentials and their first and second derivatives in Cartesian coordinates were established. These relations are useful for the study of electronic structure and electron-nuclei interaction properties of atoms, molecules, and solids by Hartree–Fock–Roothaan and correlated theories. The formulas obtained are valid for arbitrary principal quantum numbers, screening constants and locations of STOs.     

Thiazole and benzothiazole derivatives of cytisine

Several new derivatives were prepared by reacting N-1(5-R-thiazol-2-yl)-2-chloroacetamides and N-1(6-R-benzothiazol-2-yl)chloroacetamides with cytisine. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 379–380, July–August, 2006.     

Ozonolytic transformations of olefinic derivatives of L-menthol and ricinolic acid

Ozonolysis and reduction of olefinic derivatives of ricinolic acid and L-menthol were studied using hydroxylamine hydrochloride and sodium trisacetoxyborohydride to reduce the peroxide products. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 515–518, November–December, 2006.     

Water-soluble sterol derivatives

Methods have been developed for obtaining water-soluble cholesterol and sitosterol derivatives which consist in the reaction of the sterol chloroformate with dimethyl aspartate followed by saponification or in the reaction of the sterol with anhydroacetylcitric acid chloride and hydrolysis. Institute of Experimental Medicine, Academy of Sciences of the USSR, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 655–657, September–October, 1980.     

Modified coumarins. 23. Synthesis and structure of cyclohexyldihydroxanthyletin derivatives

Cyclohexyldihydroxanthyletin derivatives with S and N in place of the exocyclic O atom were synthesized. The structures of the products were proved by NMR correlation spectroscopy. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 531–533, November–December, 2006.     

Trifluoromethyl derivatives of cerium endohedral metallofullerenes

A method was developed for the synthesis of trifluoromethyl derivatives of endohedral metallofullerenes (EMF) encapsulating cerium based on the high-temperature solid-state reaction of silver trifluoroacetate with a DMF extract of EMF enriched with Ce@C₈₂. The trifluoromethyl derivatives Ce@C₈₂(CF₃)₅ (isomers I–III) with high purity (98–99%) were synthesized and isolated for the first time. These compounds were characterized by HPLC, S8-MALDI-TOF mass spectrometry, and optical spectroscopy.     

Acidic isomerization of alantolactone derivatives

A series of derivatives of the natural sesquiterpene lactones alantolactone (1) and isoalantolactone (2) was prepared. The α-methylene-γ-lactone moiety was retained in the structures of these for further modifications using reactions that affected exclusively the nonconjugated double bonds of the decalin ring. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 325–330, July–August, 2006.     

Selective reduction of 1,4-diarylimidazoline-3-oxides to imidazolidin-1-ols and hydroxylamine derivatives

Abstract  

C-2-unsubstituted imidazoline-3-oxides were reduced with NaBH₄ in THF to give the corresponding trans-3,5-diarylimidazolidin-1-ols, while under the same conditions C-2-substituted derivatives gave the corresponding ring–chain–ring tautomers. Treatment of the crude reaction mixture from the reduction of C-2-unsubstituted imidazoline-3-oxides with a MeOH–H₂O mixture provided reductive C–N bond cleavage to give hydroxylamines, while under the same conditions ring–chain–ring tautomers remained unchanged.     

The chemistry of naphthazarin derivatives

In water-containing organic solvents 2-oxo-2,3-dihydronaphthoquinone derivatives are hydrated to give the corresponding 2,2-dihydroxy-2,3-dihydronaphthoquinones. The hydration is reversible; in some cases, a keto-gem-diol equilibrium is established. The susceptibility of 2-oxo-2,3-dihydronaphthoquinone derivatives for hydration depends on the donor-acceptor properties of substituents at C(3), C(6), and C(7), on whether or not hydroxy groups are present at C(5) and C(8), and on the organic solvent basicity. For Part 5, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya. No. 3, pp. 465–470, March, 2000.     

Modified coumarins. 20. Furocoumarin derivatives of cytisine

Cytisine derivatives modified by furocoumarins were synthesized using activated esters. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 230–232, May–June, 2006.