Synthesis and characterization of new poly[phenylquinoxaline(ether)imides]

A series of new aromatic poly[phenylquinoxaline(ether)imides] were synthesized by solution polycondensation of aromatic diamines containing preformed phenylquinoxaline groups with dianhydrides having ether linkages and isopropylidene or hexafluoroisopropylidene units. All polymers are readily soluble in polar organic solvents (N-methylpyrrolidinone, DMF, dimethylacetamide) and in less polar liquids such as chloroform. Very thin coatings were deposited onto silicon wafers. According to atomic force microscopy, they had a smooth, pinhole-free surface. The polymers showed high thermal stability with decomposition temperatures above 470 °C and glass transition temperatures in the range of 210–238 °C, being thus characterized by a large gap between the glass transition and decomposition temperatures.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th year anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1952–1957, September, 2004.     

Synthesis of cyclopentane building blocks via an intramolecular CH insertion reaction of a chiral pool derived α-diazo-γ-hydroxy-β-ketosulfone

A highly functionalized cyclopentanone building block 13 was prepared by a facile Rh-catalyzed intramolecular CH insertion reaction of an enantiopure α-diazo-γ-hydroxy-β-ketosulfone 12, in turn derived from an α-hydroxy acid 2. A cyclic γ-hydroxy vinyl sulfone 16 was also prepared from 13.     

Synthesis, structure, and electrochemical properties of 12,42-dioxo-21,31-diphenyl-7,10,13-trioxa-1,4(3,1)-diquinoxalina-2(2,3),3(3,2)-diindolizinacyclopentadecaphane

The oxidative dehydrocyclization of the 3-(indolizin-2′-yl)-2-oxoquinoxaline monopodand performed either electrochemically or under the action of molecular iodine affords new redox-active heterocyclophane consisting of the redox-switchable biindolizine fragment combined with the polyether-bridged π-deficient quinoxaline systems. The single-crystal X-ray diffraction study showed that the trioxaundecane chain of heterocyclophane adopts an extended conformation, and one of the phenyl substituents of the molecule closes the pseudocavity formed by the spacer from one of the sides. The cyclic voltammetric study of heterocyclophane in MeCN and DMF showed the three-step oxidation of the indolizine fragments accompanied by the single-electron transfer in each step. The first and third steps are reversible, and the second step is irreversible. The oxidation at potentials of the first peak gives rise to stable radical cations detected by the ESR method (g = 2.0024, a _2N = 0.26 mT). Dedicated to Professor E. A. Berdnikov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1991–2003, October, 2007.     

Propanal in the Syntheses of Alkyl-substituted 3-Cyano-2-piperidone, 3-Cyano-2,5,6,7-tetrahydropyrindin-2(1H)-one, and 3-Cyanopyridine-2(1H)-thione

Condensation of propanal with cyanothioacetamide and morpholine gave 3-cyano-4-ethyl-5-methyl-6-morpholino-2-piperidone, the structure of which was studied by X-ray analysis. Reaction of propanal with cyanothioacetamides and cycloalkanone enamines gave 3-cyano-4-ethyl-2,5,6,7-tetrahydropyrindin-2(1H)-one and 3-cyano-4-ethyl-5,6-hexamethylenepyridine-2(1H)-thione. The latter was used for the preparation of substituted 2-benzyloxycarbonylmethylthiopyridine and 3-amino-2-benzyloxycarbonylthieno[2,3-b]pyridine. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1053–1059, July, 2005.     

2-(8-羟基喹啉-5-磺酸-7-偶氮)-1,8-二羟基-3,6-萘二磺酸与牛血清白蛋白的相互作用

用平衡透析法和分光光度法研究了 2 (8 羟基喹啉 5 磺酸 7 偶氮 ) 1,8 二羟基 3,6 萘二磺酸与牛血清白蛋白 (BSA)在酸性溶液中的结合反应 ,认为 8Q5SAC与BSA之间的结合力是以静电引力为主的非共键作用力 ,并探讨了其结合模型。在 2 98K下 ,测得这一反应的最大结合数为 35～ 40 ,结合常数为 6 .1× 10 5L mol。还研究了溶液基本条件如酸度和离子强度等对 8Q5SAC与牛血清白蛋白分子复合物形成的影响 ,在pH =3.34条件下 ,标准工作曲线的线性范围为 0 .2 0～ 46 .90mg L。     

Synthesis and degradation of intelligent hydrogels containing polyacetal segments

Intelligent hydrogels were first obtained by copolymerization of telechelic poly(1,3-dioxolane) (pDXL) with acrylic acid, acrylamide, N-isopropylacrylamide respectively. The synthesis and characterization of the networks were discussed. The swelling behavior of the hydrogel was dependent on the solubility parameter of the solvents and hydrogels. The networks containing polyacetal segments (pDXL) can degrade by acid in different solvents. DXL and few other cycle molecules measured by GC-MS analysis were formed after degradation. According to the degradation products, the polymerization mechanism can be testified.     

Synthesis and electrochemistry of Group 6 tetracarbonyl (N,N′-bis(ferrocenylmethylene)ethylenediamine)metal(0) complexes

Thermal substitution reaction of Cr(CO)₄(η^2:2-1,5-cyclooctadiene), Mo(CO)₄(η^2:2-norbornadiene), and W(CO)₅(η²-bis(trimethylsilyl)ethyne) with N,N′-bis(ferrocenylmethylene)ethylenediamine (bfeda) yields M(CO)₄(bfeda) complexes which could be isolated from the reaction solution and characterized by elemental analysis, MS, IR, and NMR spectroscopy. In the case of tungsten, W(CO)₅(bfeda) is formed as intermediate and then undergoes the ring closure reaction yielding the ultimate product W(CO)₄(bfeda). The electrochemical behavior of the M(CO)₄(bfeda) complexes was studied by using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) in dichloromethane with tetrabutylammonium tetrafluoroborate as electrolyte. Constant potential electrolysis of the complexes was performed successively at their peak potentials at 0 °C in their CH₂Cl₂ solution and the electrolysis was followed by in situ recording the electronic absorption spectra in every 5 mC. In the electrolysis of Cr(CO)₄(bfeda), the central Cr(0) is oxidized first and electrolysis continues with oxidations of two ferrocenyl groups until the end of totally three moles of electron passage per mole of complex. In the electrolysis of Mo(CO)₄(bfeda) and W(CO)₄(bfeda) the first oxidation occurs on the central atom forming a short-lived species which undergoes an intramolecular one-electron transfer and is reduced back to M(0) while one of the ferrocene units is oxidized to the ferrocenium cation at the same time. This indicates that the electron is transferred from iron to the central metal atom.     

Effect of initiators on grafting in the initial stage of the emulsion polymerization of methyl methacrylate using poly(vinyl alcohol) as a protective colloid

 To make clear the reason of unsuitability of poly(vinyl alcohol) (PVA) protective colloid for the emulsion polymerization of conjugated monomers, a model experiment of emulsion polymerization of methyl methacrylate (MMA) was carried out with ammonium persulfate (APS) or azobis(isobutyronitrile) (AIBN) initiators, where a small amount of MMA (1/100th of the concentration compared with ordinary emulsion polymerization) was employed. This corresponds to the initial stage of the emulsion polymerization. Grafting of MMA onto PVA took place remarkably irrespective of the kind of the initiators. Formation of homo-poly(MMA) was observed to a small extent. The formation of new emulsion particles smaller than 100 nm continued to increase to almost the end of the polymerization. PVA molecules in the grafted polymer are supposed to act as stabilizers of newly formed particles. From kinetic treatment using the experimental data, the important issues were derived as follows. Firstly, the sulfate anion radical from APS is much more reactive than the isobutyronitrile radical from AIBN in terms of hydrogen abstraction from PVA. Secondly, high grafting ability of the latter initiator system, notwithstanding the much lower reactivity in the hydrogen abstraction compared with the APS system, is attributed to the relative reactivity of the primary radicals, i.e., hydrogen abstraction reaction from PVA to initiation reaction with MMA. The much slower rate of addition of the isobutyronitrile radical to the monomer compared with that of hydrogen abstraction from PVA facilitates the grafting, although the rate constant of hydrogen abstraction is far smaller than that with the sulfate anion radical by 10⁻⁴ times. Received: 26 April 2001 Accepted: 6 September 2001     

2-(10-Diazo-10H-anthracen-9-ylidene)-malonodinitrile: A convenient precursor of 9,10-disubstituted anthracenes

Summary The acid promoted decomposition of 2-(10-diazo-10H-anthracen-9-ylidene)-malonodinitrile in the presence of water, methanol, ethanol, acetic and propionic acid, ethyl thioglycolate,p-thiocresole, and acetyl acetone yielding 9,10-disubstituted 9,10-dihydroanthracenes was investigated. Treatment of the reaction products with tri-ethyl amine followed by hydrochloric acid caused their tautomerization to the corresponding 9,10-disubstituted anthracenes. A mechanism for this reaction is proposed. The first example of an intermolecular C-C-bond formation during the protic acid promoted decomposition of a diazo compound in the presence of CH-acids was found. An improved procedure for the preparation of the starting diazo compound, which may serve as a convenient precursor of 9,10-disubstituted anthracenes, is described.Cordially dedicated to Prof. Dr.K. Winsauer on the occasion of his 70^th birthday     

Beiträge zur Chemie der Alkylverbindungen von Übergangsmetallen. 59. Cyclopentadienyl-2-(dimethylaminomethyl)ferrocenyl-Verbindungen elektronenarmer 3 d-Elemente

Contributions to the Chemistry of Transition Metal Alkyl Compounds. 59. Cyclopentadienyl-2-(dimethylaminomethyl)ferrocenyl Compounds of Early 3 d-Elements Compounds of the type (C₅H₅)₂M(FcN) (M = Sc ( 1 ), Ti ( 2 ), V ( 3 ), Cr ( 4 ); FcN = 2-dimethylaminomethyl)ferrocenyl group), and (C₅H₅)M(FcN)₂ (M = Ti ( 5 ), Cr ( 6 ) were synthesized and investigated. A detailled characterization with respect to the existence of chelate structures was realized by the uv-vis, ¹H-n.m.r. spectroscopic measurements and determination of magnetic moments.