Pentafluorophenyl derivatives of chlorine trifluoride

A reaction between C₆F₅Cl and elemental fluorine under pressure produced pentafluorophenylchlorine(III)difluoride⁽¹⁾ and 1,2-difluoro-1,2-bis(pentafluorophenyl)dichlorane, C₆F₅Cl(F)Cl(F)C₆F₅.The dichlorane was a stable colorless liquid with a boiling point of 121 – 123°. Its characterization by elemental analysis, IR, NMR and Mass Spectra will be presented. It is believed to be the first stable compound with a chlorine-chlorine bond and may be considered to be a derivative of the unknown Cl₂F₄.     

Reactions of azoles with tetrachloro-1,2-difluoroethane and 1,2-dichlorodifluoroethylene

Tetrachloro-1,2-difluoroethane reacted with pyrazole and imidazole sodium salts to give mixtures of the corresponding N-(1,2,2-trichloro-1,2-difluoroethyl) derivatives and (E)-1,2-difluoro-1,2-dihetarylethenes. (E)-1,2-Difluoro-1,2-di(3,5-dimethyl-1H-pyrazol-1yl)ethene was also obtained as a result of replacement of chlorine atoms in 1,2-dichloro-1,2-difluoroethene. Analogous reaction with more nucleophilic imidazole involved replacement of not only chlorine but also fluorine atoms in 1,2-dichloro-1,2-difluoroethene, yielding tetraimidazolyl-substituted ethylene.     

Crystal Structure of 2-[2-hydroxy-3-methoxyphenyl]-3-[2-hydroxy-3-methoxybenzylamino]-1,2-dihydroquinazolin-4(3H)-one and the Synthesis, Spectral and Thermal Investigation of its Transition Metal Complexes

A new 1,2-dihydroquinazolin-4(3H)-one ligand, 2-[2-hydroxy-3-methoxyphenyl]-3-[2-hydroxy-3-methoxybenzylamino]-1,2-dihydroquinazolin-4(3H)-one (Hmpbaq), formed by the condensation of 2-aminobenzoylhydrazide with 2-hydroxy-3-methoxybenzaldehyde and its copper(II), nickel(II), cobalt(II), manganese(II), zinc(II) and cadmium(II) complexes, have been synthesized. Their structures have been elucidated on the basis of elemental analyses, conductance measurements, magnetic moments, spectral (i.r., ¹H-n.m.r., u.v.–vis., e.p.r. and FAB-mass) and thermal studies. The formation of 1,2-dihydroquinazolin-4(3H)-one rather than hydrazone in the reaction of 2-aminobenzoylhydrazide with 2-hydroxy-3-methoxybenzaldehyde is confirmed by the ¹H-n.m.r. spectra and single crystal X-ray diffraction studies. The tridentate behavior of the ligand was proposed on the basis of spectral studies. X-band e.p.r. spectra of the copper(II) and manganese(II) complexes in the polycrystalline state at room temperature and liquid nitrogen temperature were recorded and their salient features are reported. Thermal stabilities of the manganese(II) and zinc(II) complexes have been studied.     

Synthesis and Characterization of Novel Chiral (1R,2R)-1,2-Bis[5-(Aminomethylphospinic Acid)-1,3,4-Thiadiazol-2-YL]Ethane-1,2-Diols

Abstract

(1R,2R)-1,2-bis[5-(arylideneamino)-1,3,4-thiadiazol-2-yl]ethane-1,2-diol (2a–d) were synthesized by using appropriate aldehydes and (1R,2R)-1,2-bis(5-amino-1,3,4-thiadiazol-2-yl)ethane-1,2-diol (1) as a starting compound. Then, the phosphinic acid component (3a–d) were obtained from (2a–d) and hypophosporus acid. In addition, the structures of the novel chiral compounds (2a–d) and (3a–d) were confirmed by elemental analyses, IR, ¹H-NMR, ¹³C-NMR, and ³¹P-NMR spectra.

¹H NMR and ¹³C NMR spectra for 1, 2a, and 3a (Figures S1–S6) are available online in the Supplemental Materials.     

Synthesis,antimicrobial, and mitotic toxicity evaluation of new 6-substituted 2-(benzo[4,5]imidazo[1,2-c]quinazolin-5(6H)-yl)acetic acids

A series of novel 6-substituted 2-(benzo[4,5]imidazo[1,2-c]quinazolin-5(6H)-yl)acetic acids were synthesized and characterized by ¹H, ¹³C, ¹⁹F NMR, ¹H-¹H-COSY, ¹H-¹³C-HSQC, NOESY, LC-MS, IR, and elemental analysis. The mitotic toxicity of the synthesized compounds was determined according to the Allium test procedure. The 2-(6-(pentafluorophenyl)benzo[4,5]imidazo[1,2-c]quinazolin-5(6H)-yl)acetic acid inhibited mitotic spindle formation, which resulted in significant cytotoxic effect for meristematic cells of Allium cepa l . roots. In a preliminary antimicrobial evaluation, only Streptococcus pyogenes and Candida albicans were slightly susceptible to some of the synthesized compounds.     

1,2-Bis-[(5-methyl/chloro/nitro)-2-1H-benzimidazolyl]-1,2-ethanediols and their PdCl2 complexes

1,2-Bis-[(5-methyl)-2-1H-benzimidazolyl]- (L ¹), 1,2-bis-[(5-chloro)-2-1H-benzimidazolyl]- (L ²), 1,2-bis-[(5-nitro)-2-1H-benzimidazolyl]-1,2-ethanediol (L ³) and their PdCl₂ complexes were synthesized and characterized by elemental analysis, molar conductivity, i.r. and ¹H-n.m.r. spectra. The benzene ring substituents lead to a decrease in melting point. The methyl group reduces the solubility and the acidity of L ¹ and Pd(L ¹)Cl₂, whereas the Cl and NO₂ groups increase the solubility and the acidity of L ², L ³, Pd(L ²)Cl₂ and Pd(L ³)Cl₂. In Pd(L ¹)Cl₂ and Pd(L ²)Cl₂ complexes, the ligands act as a bidentate through two nitrogen atoms. In Pd(L ³)Cl₂, ligand coordination occurs through one OH group oxygen atom and one of the benzimidazole nitrogen atoms.     

离子液体中6-(2,3-环氧丙氧基)-2(1H)-喹啉酮及其衍生物的合成

6-(3-氨基-2-羟基丙基)-2-(1H)-喹啉酮衍生物被发现具有新的正性肌力的活性. 设计合成了一系列新的氨丙醇类喹啉酮化合物. 首先研究了6-羟基-2-(1H)-喹啉酮环氧化物2在离子液体中的合成, 该反应后处理简便, 收率高, 对环境友好. 然后用合成得到的2-(1H)-喹啉酮环氧化合物在离子液体中与一系列具有生物活性的有机碱反应, 合成了氨丙醇类2-(1H)-喹啉酮化合物3. 然后由6-羟基-2-(1H)-喹啉酮出发, 在离子液体中, 进行了一锅法合成氨丙醇类2-(1H)-喹啉酮化合物的研究. 制得的2b, 3b～3f 6个新化合物用IR, ¹H NMR, MS和元素分析进行了结构表征.     

1,2-Bis-(2-benzimidazolyl)-1,2-ethanediol and 1,4-bis-(2-benzimidazolyl)-1,2,3,4-butanetetraol PdCl2 complexes

The 1,2-bis-(2-benzimidazolyl)-1,2-ethanediol (EH₂) and 1,4-bis-(2-benzimidazolyl)-1,2,3,4-butanetetraol (TH₄) ligands form 4-coordinate mono- and bi-metallic complexes with PdCl₂, respectively. In Pd(EH₂)Cl₂ the ligand acts as a bidentate through two of the nitrogen atoms. On the other hand, in Pd₂(TH₄)Cl₄ the ligand coordinates to two palladium atoms through both bis-benzimidazole nitrogen atoms and two oxygen atoms of the hydroxy groups, forming two different isomers. The complexes were characterised by analytical data, magnetic susceptibility, molar conductivity, and also by i.r., ¹H- and ¹³C-n.m.r. spectra.     

Reactions of 1,2-dihaloethanes with chalcogenide anions

Reactions of 1,2-dihaloethanes with chalcogenide anions generated from elemental chalcogens and dimethylchalcogens were performed in the hydrazine hydrate-KOH system. The use of anions Se _x ^2? and Te _x ^2? (x = 1?4) resulted in ethylene evolution and chalcogen regeneration (or in increased x value in an anion). Oligomers of Thiokol type formed only in the reaction of the 1,2-dichloroethane with a mixture of potassium disulfide and diselenide. The reductive cleavage of oligomers obtained in the hydrazine hydrate-KOH system followed by methylation led to the formation of 1,2-bis(methylthio)ethane, 1-methylseleno-2-methylthioethane, and 1,2-bis(methylseleno)ethane. The features of substitution with chalcogenide anions in vicinal dihalides are discussed. Mass spectra of compounds obtained were measured and analyzed.     

Preparation and characterization of Co(II), Ni(II) and Cu(II) complexes of a ligand containing 1,3,4-thiadiazole groups

(1R,2R)-1,2-bis-(5-amino-1,3,4-thiadiazole-2-yl)ethane-1,2-diol (L) has been prepared by the reaction of thiosemicarbazide with (2R,3R)-(+)-tartaric acid (I) and phosphorous oxychloride, and its complexes with Co(II), Ni(II) and Cu(II) have been obtained. The structures of the ligand and its complexes have been established by i. r., ¹H- and ¹³C-n.m.r. spectra, u.v.–vis–nir spectroscopy, elemental analyses, T.g.-D.t.a. and magnetic susceptibility measurements.     

Synthesis of (1<Emphasis Type="Italic">R</Emphasis>,2<Emphasis Type="Italic">R</Emphasis>)-1,2-bis-(5-(4-hydroxynaphthalen-1-ylazo)-[1,3,4]thiadiazol-2-yl)-ethane-1,2-diol

In this study, (1R,2R)-1,2-bis-(5-amino-1,3,4-thiadiazol-2-yl)ethane-1,2-diol (2), was synthesized by using (2R,3R)-(+)-Tartaric acid (1) as starting compound. Then the diazo component 3 was obtained from 2 and 1-naphthol. In addition, the structures of the synthesized compounds 2 and 3 were confirmed by elemental analyses, IR, ¹H-NMR, and ¹³C-NMR spectra. __________ Published in Kimiya Prirodnikh Soedinenii, No. 5, pp. 465–466, September–October, 2005.     

A One‐Pot Synthesis of 1,2‐Dihydroisoquinoline Derivatives from Isoquinoline via a Four‐Component Reaction

A four‐component reaction for the synthesis of 1,2‐dihydroisoquinoline derivatives is described. The Huisgen 1,4‐dipolar intermediate, which is produced from isoquinoline and an electron‐deficient acetylene compound 1 , reacts with H₂O in the presence of diketene to produce 1,2‐dihydroisoquinoline derivatives 2 (Scheme 1). In addition, reaction of isoquinoline, dibenzoylacetylene (=1,4‐diphenylbut‐2‐yne‐1,4‐dione), and diketene in the presence of H₂O leads to pyrroloisoquinoline derivative 7 . The structures of the compounds 2a – f and 7 were corroborated spectroscopically (IR, ¹H‐ and ¹³C‐NMR, EI‐MS) and by elemental analyses. A plausible mechanism for the reaction is proposed (Schemes 2 and 3).     

Synthesis and spectroscopic studies of nickel(II) chalcogenolates derived from 1,2-diarylchalcogenolato-o-xylene

Nickel(II) chalcogenolate complexes [Ni(L-L)₂(dppe) Cl₂] (1, 2) have been prepared in high yields by reacting 1,2-diarylchalcogenolato-o-xylene, o-C₆H₄(CH₂EAr)₂ (E = Se or Te; Ar = Ph, C₆H₄OMe-4 and C₆H₄OEt-4), generated in situ, with Ni(dppe)Cl₂ [dppe = 1,2-bis(diphenylphosphino)ethane] in benzene. The structures were established by elemental analyses, molar conductance, i.r. and Raman, electronic ¹H- and ³¹P-n.m.r. and mass spectral data. The analytical and spectroscopic data are consistent with an octahedral geometry around nickel in (1) and (2). The ³¹P-n.m.r. spectra indicate their cis configuration in solution. This revised version was published online in June 2006 with corrections to the Cover Date.     

A novel 2-C reactivity studies of 1-aroyl-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones

The 2-C, methylene group of 1-aroyl-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones (2) have been showed to possess a superior reactivity towards many of organic reagents. The naphthopyrones (2) condensed with aromatic aldehydes to give the 2-arylidine derivatives (3). Bromination of 2 gave 1,2-dibromo (4) or 5-bromo (5) derivatives depending on the reaction conditions. The base catalyzed addition or cycloaddition of naphthopyrones (2) to 4-methoxy benzalacetophenone gave the expected Michael adduct (6) or the cyclic adducts (7–9) depending on the type of catalytic base and reaction conditions. Structures of the products have been established by elemental analyses, IR and ¹H NMR spectroscopic methods.     

Diacenaphtho[1,2-c:1,2-e]-1,2-dithiin: synthesis, structure and reactivity

Diacenaphtho[1,2-c:1^′,2^′-e]-1,2-dithiin 2 was synthesized in 23% yield by the reaction of acenaphthylene with elemental sulfur at 120 °C. This reaction also afforded either diacenaphtho[1,2-b:1^′,2^′-d]thiophene 1 or diacenaphtho[1,2-b:1^′,2^′-e]-dihydro[e]-1,4-dithiin 3 depending on the reaction time. Compound 2 was desulfurized and converted to 1 under UV-vis irradiation in a benzene solution. Reaction of 2 with Pt(COD)₂ yielded the complex Pt(COD)(C₂₄H₁₂S₂) 4 (COD=1,5-cyclooctadiene) by insertion of a Pt(COD) group into the S-S bond of 2. When heated, 4 was desulfurized and converted to 1 by elimination of a (COD)PtS grouping. Compounds 1-4 were characterized crystallographically.     

Assembly of a new Keggin polyoxometalate-templated complex using flexible 1,2-bis(imidazol-1′-yl)ethane ligand

A new compound, [{Cu^I(bim)}₄{SiW₁₂O₄₀}] (1) (bim?=?1,2-bis(imidazol-1′-yl)ethane), was hydrothermally synthesized and characterized by elemental analyses, IR, TG, and single-crystal X-ray diffraction. Compound 1 is an infinite 1-D chain composed of Cu-bim coordination polymers and [α-SiW₁₂O₄₀]^4? polyanions. The electrochemical and electrocatalytic behaviors of 1-modified carbon paste electrode (1-CPE) have been studied.     

Synthesis and Characterization of a Novel Organic/Inorganic Hybrid Based on Octamolybdates and Benzimidazole Molecules [Hbenzimi]4 [(benzimi)2Mo8O26] · 2H2O (benzimi?=?benzimidazole)

A novel organic/inorganic compound [Hbenzimi]₄[(benzimi)₂Mo₈O₂₆] · 2H₂O (1) has been prepared hydrothermally and characterized by elemental analyses, i.r., x.p.s., t.g. and single crystal X-ray diffraction. The single crystal X-ray diffraction analysis reveals that compound (1) consists of the [Mo₈O₂₆]⁴⁻ cluster as the structural motif covalently linked by benzimidazole molecules and protonated benzimidazole molecules as charge compensation cations. It is interesting that the benzimidazole molecules were synthesized from 1,2-phenylenediamine and oxalic acid. The [Mo₈O₂₆]⁴⁻ polyoxoanions and organic ligands in compound (1) interact with each other via extensive hydrogen bonds to form a three-dimensional supramolecular framework.     

KF/Al2O3催化下芳醛和4-羟基喹啉-2-酮的反应研究

以芳醛和4-羟基喹啉-2-酮为原料, 在KF/Al₂O₃催化下以乙醇为溶剂, 在80 ℃合成了一系列新的双(4-羟基-2-氧代喹啉-3-基)-芳基甲烷衍生物, 反应条件温和, 产率较高, 并通过IR, ¹H NMR和元素分析确证产物的结构.     

Electrochemical study of 1,2-Naphthoquinone-4-sulphonate and 1,2-Naphthoquinone semicarbazone

Summary A study of the electrochemical characteristics of 1,2-naphthoquinone-4-sulphonate, sodium salt, and of the semicarbazone of 1,2-naphthoquinone (Naftazone) was carried out using d.c., a.c. and d.p. polarography and cyclic voltammetry. Changes in the waves as a function of concentration and pH indicate evidence of adsorption phenomena at the potential of the reduction wave. These techniques also indicate the formation of a mercury derivative in the case of Naftazone. The quantitative determination of these two compounds is possible by polarography. Limits of detection are 5×10^–6 and 5×10^–8 M, respectively.

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Elektrochemische Untersuchung von 1,2-Naphthochinon-4-sulfonat und 1,2-Naphthochinon-semicarbazon

Zusammenfassung Die elektrochemischen Eigenschaften von 1,2-Naphthochinon-4-sulfonat und -semicarbazon (Naftazon) wurden mit Hilfe der Gleichstrom-, Wechselstrom und Differentialpuls-Polarographie sowie der cyclischen Voltammetrie untersucht. Veränderungen an den Stufen in Abhängigkeit von Konzentration und pH-Wert deuten auf Adsorptionsvorgänge beim Potential der Reduktionsstufe hin. Im Falle von Naftazon wurde die Bildung eines Quecksilberderivats nachgewiesen. Beide Substanzen können polarographisch mit Nachweisgrenzen von 5×10^–6 bzw. 5 × 10^–8 M bestimmt werden.

     

Nitrogen bridgehead compounds. Part 86. Synthesis and reactivity of 7,12-dihydropyrimido[1′,2′;1,2]pyrido[3,4-b]indol-4(6H)-ones. Debenzologues of rutaecarpine alkaloids

A series of 7,12-dihydropyrimido[1′2′:1,2]pyrido[3,4-b]mdole-4(6H)-ones was prepared by Fischer indolization of 9-arylhydrazono-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrirmdin-4-ones. Quantum chemical calculations (ab initio and AM1) indicate that position 3 of 7,12-dihydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indole-4(6H)-one can be involved in electrophilic substitutions, while position 2 is sensitive towards nucleophilic attack. Bromination of 6-methyl-7,12-tetrahydropyrimido[1′,2′:1,2]pyrido-[3,4-b]indol-4(6H)-one 16 with bromine afforded 3-bromo derivative 25 , which was reacted with cyclic amines to give 2-ammo-7,12-dihydropyrirmdo[1′2′:1,2]pyrido[3,4-b]indol-4(6H)-ones 26–30 in an addition-elimination reaction. Vielsmeier-Haack formylation of compound 16 gave 12-formyl 31 and 3,12-diformyl 32 derivatives (an N-formyl-1-deaza derivative of nauclefidine alkaloid 34 ) at 60° and 100°, respectively. 3,12-Diformyl compound 32 was oxidized to 3-carboxyl derivative 33 with potassium permanganate. The quaternary salt 35 , obtained from compound 16 with dimethyl sulfate, suffered a ring opening on the action of aqueous sodium hydroxide. The new compounds have been characterized by elemental analyses uv, ¹H nmr and in some cases by ¹³C ruler, CD spectra and X-ray investigations.