Synthesis of novel bis(chromenes) and bis(chromeno[3,4-C]pyridine) incorporating piperazine moiety

Novel bis(2-oxo-2H-chromene) as well as bis(2-imino-2H-chromene) derivatives incorporating piperazine moiety were prepared by the cyclocondensation reaction of bis(2-hydroxybenzaldehyde) with two equivalents of each of the appropriate β-ketoesters or acetonitrile derivatives. The bis(2-imino-2H-chromene-3-carbothioamide) derivative was used as a key synthon for construction of novel bis(3-(4-substituted thiazol-2-yl)-2H-chromen-2-one) derivatives via its cyclocondensation with a series of the appropriate α-halocarbonyl derivatives. Moreover, the bis(2-hydroxybenzaldehyde) reacted with four equivalents of the appropriate acetonitrile derivatives to afford the corresponding bis(3H-chromeno[3,4-c]pyridine) derivatives. Elucidation of the structure of the novel bis(chromenes) bearing piperazine nucleus was established by the spectral data and elemental analyses.     

Bis(trimethylsilyl)amide und -methanide des Yttriums — Molekülstrukturen von Tris(diethylether-O)lithium-(μ-chloro)-tris[bis(trimethylsilyl) methyl]yttriat,solvensfreiem Yttrium-tris[bis(trimethylsilyl)amid] sowie dem Bis(benzonitril)-Komplex

Bis(trimethylsilyl)amides and -methanides of Yttrium — Molecular Structures of Tris(diethylether-O)lithium-(μ-chloro)-tris[bis(trimethylsilyl)methyl]yttriate, solvent-free Yttrium Tris[bis(trimethylsilyl)amide] as well as the Bis(benzonitrile) Complex The reaction of yttrium(III) chloride with the three-fold molar amount of LiE(SiMe₃)₂ (E = N, CH) yields the corresponding yttrium derivatives. Yttrium tris-[bis(trimethylsilyl)amide] crystallizes in the space group P3 1c with a = 1 636,3(2), c = 849,3(2) pm, Z = 2. The yttrium atom is surrounded trigonal pyramidal by three nitrogen atoms with Y? N-bond lengths of 222 pm. Benzene molecules are incorporated parallel to the c-axes. The compound with E = CH crystallizes as a (Et₂O)₃LiCl-adduct in the monoclinic space group P2₁/n with a = 1 111,8(2), b = 1 865,2(6), c = 2 598,3(9) pm, β = 97,41(3)° and Z = 4. The reaction of yttrium tris[bis(trimethylsilyl)amide] with benzonitrile yields the bis(benzonitrile) complex, which crystallizes in the triclinic space group P1 with a = 1 173,7(2), b = 1 210,3(2), c = 1 912,4(3) pm, α = 94,37(1), β = 103,39(1), γ = 117,24(1)° and Z = 2. The amido ligands are in equatorial, the benzonitrile molecules in axial positions.     

Synthesis of new bis[p-(phenylethynyl)phenyl]hetarylenes and bis[p-(phenylglyoxalyl)phenyl]hetarylenes

A series of new bis[p-(phenylethynyi)phenyl]hetarylenes was obtained by cross-coupling between heteroaromatic dibromides and phenylacetylene catalyzed by phosphine complexes of palladium in the presence of Cul and an organic base. Bis[p-(phenylethynyl)phe-nyl]hetarylenes were oxidized to the corresponding bis[p-(phenylglyoxalyl)phenylihetarylenes using the I₂-DMSO system.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2359–2361, September, 1996.     

Reactions of 5-[3-(trifluoromethyl)-phenyl]furan-2-carbaldehyde

The Knoevenagel condensations of 5-[3-(trifluoromethyl)phenyl]furan-2-carbaldehyde with seven compounds containing an active methyl or methylene group have been studied. The compounds used were: methyl 2-cyanoacetate, malononitrile, 2-furylacetonitrile, acetophenone, 2-thioxo-1,3-thiazolidin-4-one (rhodanine), 5,5-dimethylcyclohexane-1,3-dione (dimedone), and methyl 2-azidoacetate. The effect of microwave irradiation on the condensation reactions was studied and compared with “’classical”’ conditions. Thermolysis of methyl 2-azido-3-{5-[3-(trifluoromethyl)phenyl]-2-furyl}propenoate afforded methyl 2-[3-(trifluoromethyl)phenyl)]-4H-furo[3,2-b]pyrrole-5-carboxylate. (2E)-3-{ 5-[3-(Trifluoromethyl)phenyl]-2-furyl}propenoic acid was converted to the corresponding azide, which was cyclized on heating into 2-[3-(trifluoromethyl)phenyl)]-4,5-dihydrofuro[3,2-c]pyridin-4-one. The latter after successive action of POCl₃ and NH₂NH₂-Pd/C gave 2-[3-(trifluoromethyl)-phenyl]furo[3,2-c]pyridine. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 825–831, June, 2006.     

Improved synthesis of bis[p-(phenylethynyl)phenyl]hetarylenes

Bis[p-(phenylethynyl)phenyl]hetarylenes were synthesized in high yields by an improved method using cross-coupling between phenylacetylene and 4,4′-dibromobenzil followed by condensation of the 4,4′-di(phenylethynyl)benzil obtained with eithero-phenylenediamine and 3,4-diaminobenzoic acid or with benzaldehyde andp-nitrobenzaldehyde in the presence of ammonium acetate. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1889–1890, October, 1997.     

3,6-Di-tert-butyl-o-benzosemiquinone complexes of copper(1) with bidentate bis(diphenylphosphine) ligands. Synthesis, structures, and properties

New mononuclear 3,6-di-tert-butyl-o-benzosemiquinone complexes of copper(1) with bis(diphenylphosphine) ligands were synthesized: (DBSQ)Cu(dppe) (1) (DBSQ=3,6-di-tert-butyl-o-benzosemiquinone and dppe=1,2-bis(diphenylphosphino)ethane), (DBSQ)Cu(dppp) (2) (dppp=1,3-bis(diphenylphosphino)propane), (DBSQ)Cu(dppn) (3) (dppn=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl), and (DBSQ)Cu(dppfc) (4) (dppfc=1,1′-bis(diphenylphosphino)ferrocene). The compositions and structures of complexes1–4 were characterized by elemental analysis and electronic absorption, IR, and ESR spectroscopy. The molecular structures of complexes3 and4 were established by X-ray diffraction analysis. The reactions of elimination and replacement of neutral ligands in the coordination sphere of the complexes were studied by ESR spectroscopy. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2333–2340, November, 1998.     

(N-methyl-N-alkoxymethylaminomethyl)dialkoxysilanes and bis[N-methyl-N-(dialkoxysilylmethyl)amino]methanes

(N-methyl-N-alkoxymethylaminomethyl)-dialkoxysilanes and bis[N-methyl-N-(dialkoxymethyl)amino]methanes were first obtained by the interaction of (N-methylaminomethyl) dialkoxy-R-silanes with chloromethyl alkyl ethers in yields of 40–67% and 10–25 %, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 382–383, February, 1995.     

Synthesis of 2-[3-(trifluoromethyl)phenyl]furo[3,2-<Emphasis Type="Italic">c</Emphasis>]pyridine derivatives

2-[3-(Trifluoromethyl)phenyl]-4,5-dihydrofuro[3,2-c]pyridin-4-one (I) was prepared by a three-step synthesis. Its reaction with phosphorus sulfide rendered thione II which was methylated to 2-[3-(Trifluoromethyl)phenyl]-4-methylsulfanylfuro[3,2-c]pyridine (III). 5-Methyl-2-[3-(trifluoromethyl)phenyl]-4,5-dihydrofuro[3,2-c]pyridin-4-one (IV) was obtained by the reaction of I with methyl iodide in PTC conditions. The chlorine atom in derivate V was replaced with heterocyclic secondary amines via nucleophilic substitution and 4-substituted furopyridines VIa and VIb were thus prepared. 2-[3-(Trifluoromethyl)phenyl]furo[3,2-c]pyridine-4-carboxylic acid (VII) was obtained by hydrolysis of the corresponding carbonitrile Va.     

Synthese,Eigenschaften und Struktur von Amin-Addukten der Lithium-tris[bis(trimethylsilyl)methyl]zinkate

Synthesis, Properties, and Structure of the Amine Adducts of Lithium Tris[bis(trimethylsilyl)methyl]zincates . Bis[bis(trimethylsilyl)methyl]zinc and the aliphatic amine 1,3,5-trimethyl-1,3,5-triazinane (tmta) yield in n-pentane the 1:1 adduct, the tmta molecule bonds as an unidentate ligand to the zinc atom. Bis[bis(trimethylsilyl)methyl]zinc · tmta crystallizes in the triclinic space group P1 with {a = 897.7(3); b = 1 114.4(4); c = 1 627.6(6) pm; α = 90.52(1); β = 103.26(1); γ = 102.09(1)°; Z = 2}. The central C₂ZnN moiety displays a nearly T-shaped configuration with a CZnC angle of 157° and Zn? C bond lengths of 199 pm. The Zn? N distances of 239 pm are remarkably long and resemble the loose coordination of this amine; a nearly complete dissociation of this complex is also observed in benzene. The addition of aliphatic amines such as tmta or tmeda to an equimolar etheral solution of lithium bis(trimethylsilyl)methanide and bis[bis(trimethylsilyl)methyl]zinc leads to the formation of the amine adducts of lithium tris[bis(trimethylsilyl)methyl]zincate. Lithium tris[bis(trimethylsilyl)methyl]zincate · tmeda · 2 Et₂O crystallizes in the orthorhombic space group Pbca with {a = 1 920.2(4); b = 2 243.7(5); c = 2 390.9(5) pm; Z = 8}. In the solid state solvent separated ions are observed; the lithium cation is distorted tetrahedrally surrounded by the two nitrogen atoms of the tmeda ligand and the oxygen atoms of both the diethylether molecules. The zinc atom is trigonal planar coordinated; the long Zn? C bonds with a value of 209 pm can be attributed to the steric and electrostatic repulsion of the three carbanionic bis(trimethylsilyl)methyl substituents.     

Synthesis and stereochemical nonrigidity of isomeric Zn(ii)bis-[N-isopropyloxy(mercapto)naphthaldiminates]

Kinetics and reaction mechanisms governing inversion of the tetrahedral configuration at the metal center in the series ofbis-chelate Zn(II) complexes of 3,2-, 1,2-, and 2,1-oxy(mercapto)naphthaldimines, respectively4–6, have been studied with the use of dynamic¹H NMR spectroscopy. A polytopal rearrangement of the diagonal twist type has been found to be an energetically preferable pathway of the inversion reaction for complexes4 and5 with a ZnN₂O₂ coordination site, whereas the inversion reaction for complexes with a ZnN₂S₂ coordination site occurs by an intramolecular dissociation-recombination pathway that involves cleavage of a Zn-N coordination bond. In the case of complexes6, the inversion reaction is governed mainly by intramolecular degenerate ligand exchange reactions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11. pp. 2261–2265, November, 1995.This work was supported by the Russian Foundation for Basic Research (project No. 93-03-18692) and the International Science Foundation (grant No. RNJ 000).     

Theoretical investigation on multinuclear NMR chemical shifts of some tris(trifluoromethyl)boron complexes

Tris(trifluoromethyl)boron complexes have unusual properties and may find applications in many fields of chemistry, biology, and physics. To gain insight into their NMR properties, the isotropic ¹¹B, ¹³C, and ¹⁹F NMR chemical shifts of a series of tris(trifluoromethyl)boron complexes were systematically studied using the gauge‐included atomic orbitals (GIAO) method at the levels of B3LYP/6‐31 + G(d,p)//B3LYP/6‐31G* and B3LYP/6‐311 + G(d,p)//B3LYP/6‐311 + G(d,p). Solvent effects were taken into account by polarizable continuum models (PCM). The calculated results were compared with the experimental values. The reason that the structurally inequivalent fluorine atoms in a specific species give a same chemical shift in experimental measurements is attributed to the fast rotation of CF₃ group around the B? C(F₃) bond because of the low energy barrier. The calculated ¹¹B, ¹³C(F₃), and ¹⁹F chemical shifts are in good agreement with the experimental measurements, while the deviations of calculated ¹³C(X, X = O, N) chemical shifts are slightly large. For the latter, the average absolute deviations of the results from B3LYP/6‐311 + G(d,p)//B3LYP/6‐311 + G(d,p) are smaller than those from B3LYP/6‐31 + G(d,p)//B3LYP/6‐31G*, and the inclusion of PCM reduces the deviation values. The calculated ¹⁹F and ¹¹B chemical shieldings of (CF₃)₃BCO are greatly dependent on the optimized structures, while the influence of structural parameters on the calculated ¹³C chemical shieldings is minor. Copyright © 2009 John Wiley & Sons, Ltd.     

二(o-溴苄基)锡双(二乙基二硫代氨基甲酸)酯和二(o-氯苄基)锡双(吡咯啶二硫代氨基甲酸)酯的合成、结构及体外抗癌活性研究

二（o-溴苄基）二溴化锡和二（o-氯苄基）二氯化锡分别与N,N-二乙基二硫代氨基甲酸钠和吡咯啶二硫代氨基甲酸钠反应,合成了二（o-溴苄基）锡双（二乙基二硫代氨基甲酸）酯（1）和二（o-氯苄基）锡双（吡咯啶二硫代氨基甲酸）酯（2）。用X-射线单晶衍射测定了两个化合物的晶体结构,测试结果表明：化合物1的晶体为单斜晶系,空间群P2₁/c,晶体学参数a=1.82736（4）nm,b=0.90060（2）nm,c=1.98841（5）nm,β=114.8780（10）°,V=2.96871（12）nm³,Z=4,D_c=1.690g·cm^-3,μ（MoKα）=38.50cm^-1,F（000）=1496,R₁=0.0516,wR₂=0.1546。化合物2的晶体为单斜晶系,空间群C2/c,晶体学参数a=2.24128（4）nm,b=0.81878（2）nm,c=1.54269（3）nm,β=106.7870（10）°,V=2.71037（10）nm³,Z=4,D_c=1.623g·cm^-3,μ（MoKα）=14.65cm^-1,F（000）=1336,R₁=0.0229,wR₂=0.0565。晶体中锡原子呈六配位畸变八面体构型。对其结构进行量子化学从头计算,探讨了配合物的稳定性、分子轨道能量以及部分前沿分子轨道的组成特征。测定了配合物的热稳定性和体外抗癌活性。     

Novel organosoluble and colorless poly(ether imide)s based on 3,3‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]phthalide dianhydride and aromatic bis(ether amine)s bearing pendent trifluoromethyl groups

A novel series of colorless and highly organosoluble poly(ether imide)s were prepared from 3,3‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]phthalide dianhydride with various fluorinated aromatic bis(ether amine)s via a conventional two‐stage process that included ring‐opening polyaddition to form the poly(amic acid)s followed by cyclodehydration to produce the polymer films. The poly(ether imide)s showed excellent solubility, with most of them dissoluble at a concentration of 10 wt % in amide polar solvents, in ether‐type solvents, and even in chlorinated solvents. Their films had a cutoff wavelength between 358 and 373 nm, and the yellowness index ranged from 3.1 to 9.5. The glass‐transition temperatures of the poly(ether imide) series were recorded between 237 and 297 °C, the decomposition temperatures at 10% weight loss were all above 494 °C, and the residue was more than 54% at 800 °C in nitrogen. These films showed high tensile strength and also were characterized by higher solubility, lighter color, and lower dielectric constants and moisture absorption than an analogous nonfluorinated polyimide series. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3140–3152, 2006     

Synthesis and characterization of bis(organothiolato)mercury(ii) complexes by disproportionation of Hg2Cl2 in the presence of thiols

Mercury(I) chloride disproportionates to mercury metal and bis(organothiolato)mercury(II) in the presence of some thiols in good yields. The products were analyzed by means of ¹H?NMR and gas chromatographic–mass spectrometry (GC/MS), which indicated that the complexes are monomers in the gas phase and decomposed at elevated temperature to mercury(0) and corresponding disulfides.     

Tris[bis(trimethysilyl)amido]zinkate von Lithium und Calcium

Tris[bis(trimethylsilyl)amido]zincates of Lithium and Calcium Calcium-bis[bis(trimethylsilyl)amide] and Bis[bis(trimethylsilyl)amido]zinc yield in 1,2-dimethoxyethane quantitatively Calcium-bis{tris[bis(trimethylsilyl)- amido]zincate} · 3DME. When THF is chosen as a solvent, the two reactants and the zincate form a temperature-independent equilibrium, whereas in benzene no reaction occurs. The tris[bis(trimethylsilyl)amido]zincate anion displays characteristic ¹³C{¹H) and ²⁹Si{¹H] chemical shifts of 7 and ?8 ppm, respectively; the nature of the solvent, the cation and the complexating ligands don't influence the IR nor NMR data of the zincate anion and thus verify that [Ca(DME)₃]²⁺ and {Zn[N(SiMe_{3 2}]₃}^? appear as solvent separated ions, which is also confirmed by their insolubility in hydrocarbons.     

New organosoluble polyimides with low dielectric constants derived from bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl] diphenylmethylene

A new kink diamine with trifluoromethyl group on either side, bis[4-(2-trifluoromethyl-4-aminophenoxy)phenyl]diphenylmethane (BTFAPDM) , was reacted with various aromatic dianhydrides to prepare polyimides via poly (amic acid) precursors followed by thermal or chemical imidization. Polyimides were prepared using 3,3′, 4,4′-biphenyltetracarboxylic dianhydride(1), 4,4′-oxydiphthalic anhydride(2), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (3), 4,4′-sulfonyldiphthalic anhydride(4), and 4,4′-hexafluoroisopropylidene-diphathalic anhydride(5). The fluoro-polyimides exhibited low dielectric constants between 2.46 and 2.98, light color, and excellent high solubility. They exhibited glass transition temperatures between 227 and 253°C, and possessed a coefficient of thermal expansion (CTE) of 60-88 ppm/°C. Polymers PI-2, PI-3, PI-4, PI-5 showed excellent solubility in the organic solvents: N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), pyridkie and tetrahydrofuran (THF). Inherent viscosity of the polyimides were found to range between 0.58 and 0.72 dLg-1. Thermogravimetric analysis of the polyimides revealed a high thermal stability decomposition temperature in excess of 500°C in nitrogen. Temperature at 10 % weight loss was found to be in the range 506-563°C and 498-557°C in nitrogen and air, respectively. The polyimide films had a tensile strength in the range 75-87 MPa; tensile modulus, 1.5-2.2 GPa; and elongation at break, 6-7%.     

双2-乙酰基二茂铁合汞的合成及其晶体结构

标题化合物(C24H22Fe2HgO2)3是由2 氯汞基 1 乙酰基二茂铁与乙二胺反应得到的,其结构通过单晶X 射线衍射法确定。其晶体属三斜晶系,P 1空间群,Mr=1964 12,a=10 193(2),b=11 504(2),c=14 413(3) ,α=92 21(3),β=104 12(3),γ=102 67(3)°,V=1591 55(5) 3,Z=1,Dc=2 049mg/cm3,μ=8 583mm-1,F(000)=942,最终偏离因子为R=0 0859,wR=0 2617。该晶体中同时含有meso型及dl型分子,各分子中Hg原子的配位情况不一样。meso分子中的两个二茂铁是相互平行的,而另两分子dl型的二茂铁是相互垂直的。Hg原子以桥联形式连接两个二茂铁部分。meso型与dl型分子通过Hg O弱配位作用相连。     

Luminescent silver nitrate complexes of bis[2-(diphenylphosphano)phenyl]ether (DPEphos): Crystal structure of [Ag(DPEphos)(py2SH)2]NO3

Heteroleptic silver(I) nitrate complexes containing the bis[2-(diphenylphosphano)phenyl]ether (DPEphos) ligand and the heterocyclic thioamides pyridine-2(1H)-thione (py2SH), pyrimidine-2(1H)-thione (pymtH), 4,6-dimethylpyrimidine-2(1H)-thione (dmpymtH), 1,4,5,6-tetrahydropyrimidine-2-thione (thpymtH) or 1,3-imidazolidine-2-thione (imtH₂) have been synthesized and characterized by IR and UV-Vis spectroscopy, elemental analyses and melting point determinations. The complexes can be obtained by the addition of the thioamide ligand to an AgNO₃-diphosphane adduct in dichloromethane/ethanol solution. The molecular structure of [Ag(DPEphos)(py2SH)₂]NO₃ complex has been established by single-crystal X-ray diffraction. The structure features a tetrahedral silver(I) center with two phosphorus atoms from the chelating diphos ligand, and the exocyclic sulfur atom of two heterocyclic thioamide units. Intense blue-green emission is observed in the region 470-483 nm for all the complexes in the solid state and in solution at ambient temperature.     

New polyfunctional silicon-containing amines C6[CH2CH2SiMe(OCH2CH2NR2)2]6 (R = H,Me) and their reactions with cobalt(ii) chloride and dicobalt octacarbonyl

Hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene and hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene C₆[(NR₂CH₂CH₂O)₂SiMeCH₂CH₂]₆ (4, R = H; 5, R = Me) were prepared from hexakis(methyldichlorosilylethyl)benzene C₆(Cl₂MeSiCH₂CH₂)₆ and 2-aminoethanol or N,N-dimethyl-2-aminoethanol, respectively. Compounds 4 and 5 react with anhydrous cobalt (ii) chloride to give poorly soluble dodecachloro{hexakis[bis(2-aminoethoxy)methylsilylethyl]benzene}hexacobalt and dodecachloro{hexakis[bis(N,N-dimethyl-2-aminoethoxy)methylsilylethyl]benzene}hexacobalt {Co₆[(NR₂CH₂CH₂O)₂SiMeCH₂CH₂]₆C₆}Cl₁₂ (R = H or Me), respectively. Polyfunctional amine 4 reacts with dicobalt octacarbonyl to produce hexakis[bis(2-aminoethoxy)methylsilylethyl]benzenedicobalt(ii) tetrakis(tetracarbonylcobaltate) {Co₂[(NH₂CH₂CH₂O)₂SiMeCH₂CH₂]₆C₆}[Co(CO)₄]₄. N,N-Dimethyl-substituted polyfunctional amine 5 is lowly reactive in the reaction with Co₂(CO)₈, whereas the simplest model of this compound, viz., bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane (NMe₂CH₂CH₂O)₂SiMe₂, slowly reacts with Co₂(CO)₈ to give tris[bis(N,N-dimethyl-2-aminoethoxy)dimethylsilane]cobalt(ii) bis(tetracarbonylcobaltate) {Co[(NMe₂CH₂CH₂O)₂SiMe₂]₃}[Co(CO)₄]₂. Thermal decomposition and transformations of the resulting complexes under the action of oxygen and water were studied.