Synthesis and crystal structure of β-N-(5-methyl-4-oxo-5,6-dihydro-4H-1,3-thiazin-2-yl)isonicotinohydrazide

In the presence of amines under mild conditions, β-N-(methacryloylcarbamoythioyl)isonicotinohydrazide underwent intramolecular heterocyclization to give β-N-(5-methyl-4-oxo-5,6-dihydro-4H-1,3-thiazin-2-yl)isonicotinohydrazide, the spatial structure was confirmed by X-ray crystallography.     

Cycloaddition to 3h-1,2-dithiole-3-thiones. X-ray structural investigation of 2,3,4′,5′-tetracarbonmthoxy-5-methyl-6-phenylthio-pyran-4-spiro-2′-(1,3-dithiole)

Treatment of 4-methyl-5 -phenyl-3H-1,2-dithiole-3-thione with dicarbomethoxyaceotene gave 2,3,4,5-tetra-carbomethoxy-5-methyl-6-phenylthiopyran-4-spiro-2-(1,3-dithiole) whose structure was proved by x-ray investigation.K. A. Timiryazev Agricultural Academy, Moscow 127550. A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 908–914, July, 1994.     

Synthesis and Crystal Structure of 1′-Methyl-4′- (4-chlorophenyl)-1H-indole-3-spiro-2′-pyrrolidine- 3′-spiro-4'-(2'-phenyloxazole)-2,5'(3H,4'H)-dione

The title compound (C26H20ClN3O3) has been synthesized by 1,3-dipolar cycloaddition reaction from isatin, sarcosine and (Z)-4-(4-chlorobenzylidene)-2-phenyloxazol-5(4H)-one through a one-pot procedure, and its structure was confirmed by IR, 1H NMR, elemental analysis and single-crystal X-ray diffraction analysis. The crystal belongs to the triclinic system, space group P1, with a = 9.3903(19), b = 11.398(2), c = 12.603(3) , α = 83.495(3), β = 68.988(3), γ = 67.178(3)°, V = 1160.1(4) 3, Z = 2, Mr = 457.90, Dc = 1.311 g/cm3, μ = 0.198 mm-1, F(000) = 476, the final R = 0.0489 and wR = 0.1144 for 3109 observed reflections with I > 2σ(I).     

Electropolymerization of three-dimensional π-conjugated system based on 3,4-ethylenedioxythiophene (EDOT)

A 3D π-conjugated system obtained by grafting 3,4-ethylenedioxythiophene (EDOT) on a twisted bithiophene core has been synthesized and used as precursor for electropolymerization. Preliminary investigations of its electrochemical properties shows that it can be straightforwardly electropolymerized into an electroactive conjugated material.     

Formation of 3a′,8′-dimethyl-3a′,5′-dihydro-1′H,3′H-dispiro-[cyclohexane-1,3′-furo[3,4-f][2]benzofuran-5′,1″-cyclohexane]-1′,7′(4′H)-dione in the reaction of 3-acetyl-4-methyl-1-oxaspiro[4.5]dec-3-en-2-one with potassium hydroxide

3a′,8′-Dimethyl-3a′,5′-dihydro-1′H,3′H-dispiro[cyclohexane-1,3′-furo[3,4-f][2]benzofuran-5′,1″-cyclohexane]-1′,7′(4′H)-dione was synthesized by reaction of 3-acetyl-4-methyl-1-oxaspiro[4.5]dec-3-en-2-one with potassium hydroxide in water.     

Kinetic resolution of (±)-2,3-dihydro-3-methyl-4H-1,4-benzoxazines with (S)-naproxen

A very effective method for the preparation of the (S)-enantiomers of 2,3-dihydro-3-methyl- and 7,8-difluoro-2,3-dihydro-3-methyl-4H-1,4-benzoxazines (1a and 2a) was developed using (S)-(+)-naproxen acyl chloride as the chiral agent for kinetic resolution of racemates. This method enables one to obtain the (S)-enantiomers of benzoxazines 1a and 2a of high enantiomeric purity (99% ee) in nearly 50% yield, taking into account that the (R)-enantiomers are recycled after their racemisation.     

A competitive sensing system based on cyclobis(paraquat-p-phenylene) and a new β-cyclodextrin-tetrathiafulvalene derivative

We report the synthesis of 4,5-di(ethylthio)-4′-[6-deoxy-β-cyclodextrin-6-yl-aminocarbonyl]-tetrathiafulvalene (β-CD-DET-TTF) and its inclusion abilities towards cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺ ) and 1-naphthol. The structure of the synthesised compound has been established by mass spectrometry and ¹H NMR spectra combined with a theoretical MM3 and AM1 study. The sensor affords a charge transfer (CT) complex with the CBPQT⁴⁺  and is able to include 1-naphthol in the cyclodextrin cavity. The complexes were characterised experimentally by UV–vis spectroscopy and simulated by a MM3 docking procedure. The sensing ability of the β-CD-DET-TTF/CBPQT⁴⁺  complex towards 1-naphthol has been investigated by a competitive spectral method.

The synthesis and characterisation of a new water soluble β-CD-DET-TTF derivative able to formed a CT complex with the CBPQT⁴⁺  acceptor is reported. The water soluble CT complex β-CD-DET-TTF/CBPQT⁴⁺  could be used as an efficient sensor towards aromatic guests prone to give inclusion complexes with the CBPQT⁴⁺  ring.     

Electron density distribution in the crystal of the Meisenheimer complex of potassium 3-methyl-5′, 7′-dinitro-5′, 8′-dihydrospiro(1,3-oxazolidine-2,8′-quinolinide) based on X-ray diffraction data at 153 K

The electron density distribution in the crystal of the Meisenheimer complex of potassium 3-methyl-5′, 7′-dinitro-5′, 8′-dihydrospiro(1,3-oxazolidine-2,8′- quinolinide) (1) was studied based on the data of precision X-ray diffraction study. The experimental data were compared with the results of quantum-mechanical calculations. The electron density distributions in the regions of the nitro groups are substantially different in spite of the similarity in the geometric parameters of these groups. In addition, there is a discrepancy between the exprimental and theoretical data on this distribution. The effect of the cation on the electronic strucure of the anion in the crystalline phase is the most probable cause of the differences observed. To reveal this effect.ab initio calculations of different anion1-K⁺ systems were performed and a topological analysis of the electron density distributions was carried out. Depending on the mode of coordination of the cation to the anion, the former determines the contribution of alternative resonance forms to the structure of the anion. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 451–458, March, 2000.     

Dual-wavelength β-correction spectrophotometric determination of trace concentrations of cyanide ions based on the nucleophilic addition of cyanide to imine group of the new reagent 4-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-6(3H)-one

A simple, fast, low cost and sensitive direct β-correction spectrophotometric assay of cyanide ions based on its reaction with the reagent 4-hydroxy-3-(2-oxoindolin-3-ylideneamino)-2-thioxo-2H-1,3-thiazin-6(3H)-one, abbreviated as HOTT in aqueous media of pH 7-10 is described. The electronic spectrum of the produced brown-red colored species showed well defined and sharp peak at λ_max = 466 nm. The effective molar absorptivity for the produced cyano compound was 2.5 × 10⁴ L mol⁻¹ cm⁻¹. Beer's law and Ringbom's plots were obeyed in the concentration range 0.05-2.0 and 0.30-1.5 μg mL⁻¹ cyanide ions, respectively. The proposed method offers 16.0 and 50.3 μg L⁻¹ lower limits of detection (LOD) and quantification (LOQ) of the cyanide ion, respectively. The analytical utility of the method for the analysis of cyanide ions in tap and drinking water samples was demonstrated and the results were compared successfully with the conventional cyanide ion selective electrode. The short time response and the detection by the naked eye make the method available for the detection and quantitative determination of cyanide in a variety of samples e.g. fresh and drinking water. Moreover, the structure of the produced colored species was determined with the aid of spectroscopic measurements (UV-Vis, IR, ¹H and ¹³C NMR) and elemental analysis.     

New thiopyran-4-spiro-2′-(1,3-dithiolane):Formation mechanism and crystal structure

Ethylene trithiocarbonate reacted with dimethyl acetylenedicarboxylate to furnish tetramethyl thiopyran-4-spiro-2'-(1,3- dithiolane)-2,3,5,6-tetracarboxylate,a new thiopyran-4-spiro-2'-(1,3-dithiolane) heterocyclic compound,as the minor product together with the major product dimethyl 2-thioxo-1,3-dithiole-4,5-dicarboxylate.The new heterocycle was probably formed through a[2 + 2]cycloaddition between ethylene trithiocarbonate and dimethyl acetylenedicarboxylate followed by a 1,3-dipolar cycloaddition or[...     

Condensed isoquinolines 33*. Synthesis of 1′-R-spiro-[7H,8H-2a,7a-diazacyclopenta-[fg]naphthacene-2,4′-(1′H)-pyridine]-1,8(2H)-diones

Heating 5,13-dihydro-11H-isoquino[3,2-b]quinazolin-11-one with isonicotinoyl chloride in pyridine gives 6-isonicotinoyl-5,13-dihydro-11H-isoquino[3,2-b]quinazolin-11-one. The 1-alkyl-4[(11-oxo-5,13-dihydro-11H-isoquino[3,2-b]quinazolin-6-yl)carbonyl]pyridinium iodides obtained by alkylation of 6-isonicotinoyl-5,13-dihydro-11H-isoquino[3,2-b]quinazolin-11-one using alkyl iodides in the presence of NaH are converted to 1′-R-spiro[7H,8H-2a,7a-diazacyclopenta[fg]naphthacene-2,4′(1′H)-pyridine]-1,8(2H)-diones. The chemical and spectroscopic properties of the spiro compounds obtained were studied. For Communication 32 see [1]. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 52–58, January, 2009.     

Studies on the γ-effects. Part 3. Variations in the γ-effects ofN-substituted benzylamines,o-aminomethylphenols and 3,4-dihydro-2H-1,3-benzoxazines against theE s ′ substituent constants

The magnitude of the -effects on¹³C chemical shifts was studied as function of theN-substitution [Me, Et, Bu, CH₂C₆H₅, CH₂CH₂C₆H₅, Prⁱ, Bu^t, Bu^s, c-C₆H₁₁, CH(CH₃)C₆H₅, Bu^t, or Ph] for several benzylamines,o-aminomethylphenols and 3,4-dihydro-2H-1,3-benzoxazines. A correlation between the _c-values and the steric substituent constants (E _s ) of theN-substituents proved useful in characterizing the variation of the -effects along with the conformational factors. The diastereospecificity of the -effects is discussed for purposes of configurational assignments.For part 2, see Ref. 1. This paper is also Part 5 in the series Studies on the Benzoxazine Series.     

Novel One-Pot Multicomponent Synthesis of Substituted 2,3-Dihydro-2-(6-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazin-3-yl)phthalazine-1,4-diones and Substituted 3-[3-(N′-Benzylidene-hydrazino)-7H-[1,2,4] triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-4-hydroxy-6-methyl-pyran-2-ones

A one-pot procedure has been developed for the synthesis of substituted 2,3-dihydro-2-(6-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-7H-[1,2,4]triazolo[3,4-b] [1,3,4]thiadiazin-3-yl)phthalazine-1,4-diones by reaction of 3-(2-bromoacetyl)-4-hydroxy-6-methyl-2H-pyran-2-one, 4-amino-5-hydrazino-4H-[1,2,4]triazole-3-thiol, and phthalic anhydrides in acetic acid medium. Similarly, a one-pot, three-component synthetic procedure has been developed for substituted 3-[3-(N¹-benzylidene-hydrazino)-7H-[1,2,4]triazolo[3,4-b][1,3,4]thiadiazin-6-yl]-4-hydroxy-6-methyl-pyran-2-ones from 3-(2-bromoacetyl)-4-hydroxy-6-methyl-2H-pyran-2-one, 4-amino-5-hydrazino-4H-[1,2,4]triazole-3-thiol, and various aromatic aldehydes in absolute ethanol and a few drops of glacial acetic acid.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Synthesis of bioactive magnetic nanoparticles spiro[indoline-3,4′-[1,3]dithiine]@Ni (NO3)2 supported on Fe3O4@SiO2@CPS as reusable nanocatalyst for the synthesis of functionalized 3,4-dihydro-2H-pyran

New bioactive magnetic nanoparticles of spiro[indoline-3,4′-[1,3]dithiine]@Ni (NO₃)₂ supported on Fe₃O₄@SiO₂@CPS were synthesized in five steps. The structure of synthesized magnetic nanoparticles was identified by using Energy-Dispersive X-ray spectroscopy (EDX), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD), Thermal Gravimetric Analysis (TGA), Infrared spectroscopy (FT-IR), Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), Vibrating Sample Magnetometer (VSM) and Brunauer Emmett Teller (BET) surface analysis. Antimicrobial activity of the synthesized magnetic nanoparticles based on MIC (Minimum Inhibitory Concentration) and MBC (Minimum Bactericidal Concentration) and MFC (Minimum Fungicidal Concentration) values were also examined. Furthermore, the synthesized magnetic nanoparticles exhibited appropriate catalytic properties in the synthesis of the 3,4-dihydro-2H- pyran derivatives.     

N-(5-hydroxy-3′,4′-ethylenedioxyisoflavonyl-7-oxyacetyl)amino acids

For the purpose of seeking new biologically active compounds in the flavonoid series, a series of N-(5-hydroxy-3,4-ethylenedioxyisoflavonyl-7-oxyacetyl)amino acids was synthesized; their structure was confirmed by PMR spectral data.Taras Shevchenko Kiev University, Kiev 252033, Ukraine. Institute of Bioorganic Chemistry and Petrochemistry, Academy of Sciences of the Ukraine, Kiev 253660. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 482–486, April, 1998.     

Fluorescent sensing of anions based on excited state intramolecular proton transfer in N-(3-hydroxy-2- naphthamido)-N′-phenylthiourea

A neutral N-amidothiourea-based excited state intramolecular proton transfer (ESIPT) anion receptor bearing an o-hydroxynaphthamide fluorophore and a thiourea binding site, N-(3-hydroxy-2-naphthamide)-N’-phenylthiourea (1a), was designed and synthesized. Fluorescence and absorption response of 1a toward anions were assessed in acetonitrile. IR and NMR experiments indicated that the OH…O=C intramolecular hydrogen bond (IHB) in 1a was weak so that it only exhibited the short-wavelength normal emission other...     

5′,5′,6,6-Tetramethyl-6,7-dihydro-3′H-spiro[1,3-benzodithiole-2,1′-cyclohexane]-3′,4(5H)-dione

Russian Journal of Organic Chemistry -     

Bis(1,8-naphthylimides) and bis(1′,8′-naphthoylene-1,2-benzimidazoles) based on new bis(naphthalic anhydrides)

The reaction of bis(naphthalic anhydrides) with aniline and o-phenylenediamine under conditions of hightemperature cyclocondensation in m-cresol in the presence of a catalyst (benzoic acid) gives bis(1,8-naphthylimides) and bis(1,8-naphthoylene-1,2-benzimidazoles) which model the elementary units of polyimides and polynaphthoylenebenzimidazoles, respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 649–652, May, 1991.     

SYNTHESIS OF SPIRO [1,3-BENZODIOXOLE-2,4′-(3′H) QUINAZOLINES]

Abstract

In the present investigation, the authors could obtain a new series of spiranes (1) through the reaction of the high potential quinone tetrachloro-o-benzoquinone with 2-aryl-3-phenyl-3H-quinazoline-4-thiones. Thus, 2,3-diphenyl- (2a), 2-p-tolyl-3-phenyl- (2b) and 2-p-anisyl-3-phenyl- (2c)-3H-quinazoline-4-thiones react readily with tetrachloro-o-benzoquinone, in boiling toluene, to give the corresponding spiro-1,3-benzodioxole-2,4′-(3′H)-quinazolines (1a-c), respectively.