Synthesis of imidazo[4,5-<Emphasis Type="Italic">e</Emphasis>]benzo[1,2-<Emphasis Type="Italic">c</Emphasis>;3,4-<Emphasis Type="Italic">c</Emphasis>´]difuroxanes

A method for the synthesis of imidazo[4,5-e]benzo[1,2-c;3,4-c´]difuroxanes, potential nitric oxide donors, has been developed. The synthesized compounds were characterized by IR and NMR spectroscopy, high resolution mass spectrometry, and elemental analysis.     

Heterocycles with a bridging nitrogen atom. 15. The novel recyclization of dipyrido[1,2-<Emphasis Type="Italic">a</Emphasis>:1′,2′-<Emphasis Type="Italic">c</Emphasis>]-imidazolium salts to pyrido[1,2-<Emphasis Type="Italic">a</Emphasis>]-benzimidazole-8-carboxaldehydes

A previously unknown recyclization of an 11-acyldipyrido[1,2-a:1,2-c]imidazolium cation to 8-formyl-9-methyl(aryl)pyrido[1,2-a]benzimidazoles has been discovered. The proposed reaction mechanism includes a selective opening of one of the pyridinium rings and the formation of a benzaldehyde fragment via condensation of the intermediate with the participation of the acyl group.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 135–139, January, 2005.     

Hetero-Diels–Alder Reaction of Aroylpyrrolo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinoxalinetriones with Styrene

Hetero-Diels–Alder reaction of 3-aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones with styrene afforded diastereoisomeric (5R*,6aR*)- and (5S*,6aR*)-3,5-diaryl-5,6-dihydropyrano[4′,3′:2,3]pyrrolo[1,2-a]-quinoxaline-1,2,7(8H)-triones.     

Synthesis of New Thieno[2,3-<Emphasis Type="Italic">b</Emphasis>:5,4-<Emphasis Type="Italic">c</Emphasis>′]dipyridines

Summary. We describe the formation of thieno[2,3-b:5,4-c]dipyridines from 5,6-dihydropyridine-2(1H)-thiones. The two-step reaction mechanism was revealed by isolation of an intermediate. The oxo and thioxo groups of the obtained tricyclic compounds were hydrogenated selectively. The structures of all new compounds were elucidated by NMR experiments.Received December 17, 2002; accepted December 20, 2002 Published online June 2, 2003     

Determination of the <Emphasis Type="Italic">R</Emphasis> ⇄ <Emphasis Type="Italic">S</Emphasis> enantiomerization barrier in 5,6-dihydrobenzoimidazo[1,2-<Emphasis Type="Italic">c</Emphasis>]quinazolines

Chiral imidazoquinazolines undergoing thermally induced reversible R ⇄ S enantiomerization have been synthesized by the interaction of 2-(o-aminophenyl)benzimidazoles with aldehydes and ketones. The benzimidazole fragment has been used for the first time as an indicator group in temperature-dependent ¹H NMR spectra for determining the energy barrier of this rearrangement. The effects of nearby substituents on the kinetic and activation parameters, and on the recyclization mechanism have been investigated.     

Polynitromethyl derivatives of furazano[3,4-<Emphasis Type="Italic">e</Emphasis>]di([1,2,4]triazolo)-[4,3-<Emphasis Type="Italic">a</Emphasis>:3′,4′-<Emphasis Type="Italic">c</Emphasis>]pyrazine as components of solid composite propellants

The energetic potential of solid composite propellants (SCP) with furazano[3,4-e]di([1,2,4]- triazolo)[4,3-a:3′,4′-c]pyrazine including trinitromethyl (C(NO₂)₃), fluorodinitromethyl (CF(NO₂)₂), and (difluoroamino)dinitromethyl (C(NF₂)(NO₂)₂) groups was estimated based on thermochemical calculations. It was shown that C(NO₂)₃ and C(NF₂)(NO₂)₂ derivatives can constitute the basis of metal-free compositions of SCP with a specific impulse from 251 to 263 s, i.e., comparable or superior in efficiency to HMX-based propellants.     

Synthesis and reactivity of 2-(2-furyl)-1,7-dimethyl-1<Emphasis Type="Italic">H</Emphasis>,7<Emphasis Type="Italic">H</Emphasis>-benzo[1,2-<Emphasis Type="Italic">d</Emphasis>: 3,4-<Emphasis Type="Italic">d</Emphasis>′]diimidazole

2-(2-Furyl)-1,7-dimethyl-1H,7H-benzo[1,2-d: 3,4-d′]diimidazole was synthesized by the Weidenhagen reaction followed by N-methylation. Electrophilic substitution reactions of the title compound (nitration, bromination, sulfonation, formylation, and acylation) involved both the furan ring and central benzene fragment.     

<Emphasis Type="Italic">N</Emphasis>-arylsulfanyl-<Emphasis Type="Italic">N</Emphasis>-arylsulfonyl(acyl)-<Emphasis Type="Italic">N</Emphasis>′-phenylthiourea sodium salts

Reactions of N-arylsulfonyl(acyl)arenesulfenamide sodium salts with phenyl isothiocyanate afforded N-arylsulfanyl-N-arylsulfonyl(acyl)-N-phenylthioura sodium salts which were found to increase thermal stability of finely dispersed poly(vinyl chloride).Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 10, 2004, pp. 1532–1535.Original Russian Text Copyright © 2004 by Koval, Oleinik.     

Rhodium(I) pentasubstituted cationic complexes on the basis of 1,2-<Emphasis Type="Italic">O</Emphasis>-Alkylidene-3,5,6-<Emphasis Type="Italic">O</Emphasis>-phosphinetriyl-α-<Emphasis Type="SmallCaps">D</Emphasis>-glucofuranose

Reaction of 1,2-O-alkylidene--D-glucofuranose 3,5,6-phosphites with dicarbonylrhodium(I) acetylacetonate was studied. The structure of the reaction products is determined by the reagent ratio. At a 5:1 molar ratio, the step ligand-exchange process yields chiral complexes of the [RhL₅]⁺acac^– type. Dynamics of and anion exchange in these complexes are considered.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1418–1421.Original Russian Text Copyright © 2004 by A. Koroteev, Teleshov, M. Koroteev, and Nifantev.This revised version was published online in April 2005 with a corrected cover date.     

Thermal transformations of 7-aryl-1,6-diazabicyclo[4.10]heptanes and 6,13-diarylperhydrodipyridazino-[1,2-<Emphasis Type="Italic">a</Emphasis>: 1′,2′-<Emphasis Type="Italic">d</Emphasis>]-1,2,4,5-tetrazines

The thermolysis of 7-aryl-1,6-diazabicyclo[4.1.0]heptanes in the absence of 1,3-dipolarophiles leads to dimers of the initially formed azomethineimines, namely, 6,13-diaryloctahydrodipyridazino[1,2-a:1′,2′ Dedicated to the memory of A. A. Potekhin. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1062–1070, July, 2008.     

New photochromic 1,1,3-trimethylspiro[benzo[<Emphasis Type="Italic">e</Emphasis>]indoline-2,3′-[3<Emphasis Type="Italic">H</Emphasis>]-pyrano[3,2-<Emphasis Type="Italic">f</Emphasis>]quinoline]

A new photochromic spiropyran of the benzoindoline series containing the quinoline moiety was synthesized. Its structure was determined by IR and ¹H NMR spectroscopy. The crystal structure of the new compound was established by X-ray diffraction. The photochromic properties of the synthesized spiropyran were investigated.     

The investigations in 2,3′-biquinoline series. 25*. Synthesis of 4-(2-quinolinyl)-pyrrolo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinolines and 4-(2-quinolyl)-imidazo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinolines

A method has been developed for the synthesis of 4-(2-quinolinyl)-1,2,3,3a-tetrahydropyrrolo-[1,2-a]quinolines based on the 1,3-dipolar cycloaddition reaction of α,β-unsaturated carbonyl compounds to 2,3′-biquinolinium salts. Oxidation in benzene using MnO₂ gave 4-(2-quinolinyl)-pyrrolo[1,2-a]quinolines. It was found that a side product of the 1,3-dipolar cycloaddition is 7,14-di-benzoyl-6,13-di(2-quinolyl)-6a,7,13a,14-tetrahydro-7a,14a-diazadibenzo[a,h]anthracene. Reaction of 1′-phenacyl-2,3′-biquinolinium salts with hydroxylamine in acetic acid gave 4-(2-quinolyl)imidazo-[1,2-a]quinolines. *For Communication 24 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 433–439, March, 2009.     

Synthesis and structure of a new heterocyclic system – 7,8-dihydroimidazo- [1,2-<Emphasis Type="Italic">c</Emphasis>][1,3]thiazolo[4,5-<Emphasis Type="Italic">e</Emphasis>]pyrimidine

The purpose-directed synthesis of a new heterocyclic system, 7,8-dihydroimidazo[1,2-c][1,3]thia- zolo[4,5-e]pyrimidine has been carried out based on the successive interaction of available 2-(aroyl- aminocyanomethylene)imidazolidines with hydrogen sulfide and triethyl orthoformate with subsequent intramolecular cyclocondensation of the obtained 8-aroylamino-7-thioxo-1,2,3,7-tetrahydroimidazo- [1,2-c]pyrimidines under the action of phosphorus pentasulfide or polyphosphoric acid.     

SBR composites reinforced with <Emphasis Type="Italic">N</Emphasis>-isopropyl-<Emphasis Type="Italic">N</Emphasis>′-phenyl-<Emphasis Type="Italic">P</Emphasis>-phenylenediamine-modified clay

SBR compounds including the N-isopropyl-N’-phenyl-p-phenylenediamine-modified clay(organoclay) were prepared.Effects of modified clay and antioxidant(IPPD) contents on mechanical and rheological properties of SBR composites were studied.FTIR results confirmed that the clay was chemically modified by IPPD and changed into an organoclay.X-ray diffraction(XRD) results confirmed the increase in interlayer distance of the clay due to the insertion of IPPD.Rheological and cure characteristics of SBR compounds were determined using RPA(Rubber Process Analyzer) and rheometer.Scorch time and cure time of SBR compounds decreased with introduction of the organoclay.Mechanical properties and heat aging resistance of the SBR composites were improved significantly by incorporation of the organoclay.     

<Emphasis Type="Italic">N</Emphasis>′-tetrazolylmethoxyl derivatives of <Emphasis Type="Italic">N</Emphasis>-methyldiazene <Emphasis Type="Italic">N</Emphasis>-oxides

A preparation method was developed for previously unknown tetrazole derivatives containing in the 1, 2, and/or 5 positions of the tetrazole ring N-methyldiazene-N-oxide-N′-oxymethyl groups.     

Crystal structure of the molecular complex of 1,3,5-<Emphasis Type="Italic">tris</Emphasis>-<Emphasis Type="Italic">m</Emphasis>-chlorophenylisocyanurate with ε-caprolactone

The molecular complexes of 1,3,5-tris-m-chlorophenylisocyanurate and ε-caprolactone were synthesized by the reaction of the latter with 3-chlorophenylisocyanate in the presence of triethylamine. Single crystals were grown, and the molecular and crystal structures of the synthesized complexes were investigated.     

Production and Accumulation of 4-<Emphasis Type="Italic">O</Emphasis>-Methyl-α-<Emphasis Type="SmallCaps">d</Emphasis>-Glucuronosyl-Xylotriose by Growing Culture of Thermophilic <Emphasis Type="Italic">Anoxybacillus</Emphasis> sp. Strain JT-12

A thermophilic Anoxybacillus sp. strain JT-12, isolated from soil, produced acidic xylotriose, 4-O-methyl-α-d-glucuronosyl-xylotriose (MeGlcAX₃), as a main product from birchwood xylan and accumulated them in the culture under optimum conditions at pH 7.0 and 55 °C using 0.75% (w/v) birchwood xylan as a carbon source for 42–72 h. The acidic xylotriose was purified by ethanol precipitation and high-performance liquid chromatography using NH₂ Lichosher® 100 column. The results of electrospray ionization mass spectrometry, mass to charge ratio (m/z) 603.23, confirmed that the purified sample was acidic xylotriose that had benefits and applications in many fields.     

Facile cellulose nanofibrils amidation using a ‘<Emphasis Type="Italic">one</Emphasis>-<Emphasis Type="Italic">pot</Emphasis>’ approach

We report a ‘one-pot’ synthetic approach for TEMPO (2,2,6,6-tetramethyl-piperidin-1-oxyl) oxidized cellulose nanofibrils (TOCN) surface amidation by coupling up to 70% of superficial carboxylic units in TOCN with long alkyl chain primary amines (dodecylamine and octadecylamine) using TBTU [O-(1H-benzotriazol-1-yl)-N,N,N’,N’-tetramethyluronium tetrafluoroborate] uronium salt as coupling agent. Raw TOCNs were produced from commercial microcrystalline cellulose and have an elongated highly tangled morphology with nanometric diameters and lengths up to several micrometers with a crystallinity of 62%. TOCN´s degree of oxidation was 1.25 mmol –COOH groups/g cellulose. The TOCN-amidated products named TOCN-AMDC12 and TOCN-AMDC18 depending upon to the primary amine used for the synthesis (dodecylamine –C12– for the former and octadecylamine –C18– for the latter), were characterized using field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy with attenuated total reflectance and X-ray diffraction. After amidation the hydrated gel-like TOCNs become a cream-colored gel insoluble in water and soluble in toluene. IR data indicates formation of an amide bond after the reaction, and FESEM images suggest a slight increase in fibril width as a result of the long-chain amide derivatives grafted onto the TOCN’s surface. Thermal stability and hydrophobicity of the products were determined using thermogravimetrical analysis and contact angle (CA) measurements. The TOCN-amidated products showed improved thermal properties with maximum decomposition temperatures of 347 and 358 °C, for TOCN-AMDC12 and TOCN-AMDC18 respectively, when compared to the raw TOCN (T_d 340 °C); and high hydrophobicity with CA of 61° and 67°, respectively. Finally, the proposed method for TOCN amidation has advantages over current amidation approaches in that it is performed in aqueous media, does not require heating and occurs rapidly (2 h).     

1,3-Diamino-2-Hydroxypropane-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-Tetraacetic Acid: Crystal and Molecular Structures

The synthesis, IR spectroscopic study, and X-ray diffraction analysis (CIF file CCDC no. 1574078) are carried out for 1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetraacetic acid (I). The structural units of a crystal of compound I are (H_4.5HPdta)^0.5– anions, (H_5.5HPdta)^0.5+ cations, and molecules of water of crystallization joined by a branched network of hydrogen bonds: strong intermolecular O–H…O and intramolecular N–H…O bonds.     

Basicity of Highly Substituted β-Octaalkyl-<Emphasis Type="Italic">meso</Emphasis>-aryl- and -<Emphasis Type="Italic">meso</Emphasis>-thienyl Porphyrins

5-Phenyl-, 5,15-diphenyl-5,15-di(thiophen-2-yl)-, and 5,10,15,20-tetraphenyloctaalkyl-21H,23H-porphyrins in benzene–acetic acid mixtures are moderate bases (pK–0.27 to–2.48). There is no simple correlation between the basicity constants and any electronic or geometric structure parameter of their molecules due to the contributions of three factors to the basicity: distortion of the planar structure in highly substituted macrocycles and their protonated forms, positive charge delocalization over the conjugated bond system, and electronic effects of substituents.