PU/MOMMT纳米复合材料的制备与研究

纳米复合材料由于其纳米尺寸效应，表面效应以及纳米粒子与基体界面间强的相互作用，具有优于相同组分常规复合材料的力学、热学等性能，引起了人们的广泛关注。用纳米材料改性聚合物，制备纳米复合材料是获得高性能高分子复合材料的重要方法。1998年以来，Pinnavaia等首先制备了聚氨酯，蒙脱土（PU／MMT）纳米复合材料，研究了有机蒙脱土在聚醚中的分散性。其后Chen等将聚羟基己内酯/蒙脱土（PCL／MMT）纳米复合材料加入到PCL和二苯基甲烷-4，4＇-二异氰酸酯（MDI）合成的预聚体与1，4-丁二醇扩链反应后的溶液中，制备了PU／MMT纳米复合材料。少量PCL／MMT的引入可使复合材料的综合性能大幅提高。     

Preparation and steric structure of 3(2H)-pyridazinones and 1,2-oxazin-6-ones fused with three- to six-membered saturated carbocycles or norbornane skeleton

Summary Reactions ofcis-2-(4-methylbenzoyl)-cyclopropane- (1) and-cyclobutanecarboxylic acids (2), the stereoisomeric cyclohexyl homologues (3 and4), and di-endo-3-(4-methylbenzoyl)-bi-cyclo-[2.2.1]heptane-2-carboxylic acid (5) with hydrazines yield the cycloalkane-condensed (3(2H)-pyridazinones6–9 and the norbornane di-endo-fused derivatives10. With hydroxylamine, compounds1 and3–5 were transformed to the cycloalkane- and norbornane-condensed 1,2-oxazin-6-ones11–14. Transformation of3–5 led to thetrans-hexahydroanthrone17a and its methylene-bridged analogue24. From the stereoisomeric hexahydro-1(3H)-isobenzofuranones20 and21, the partly saturated anthrones were also prepared; the products (16b and17b) contain the methyl substituent in position 6. On reduction,16b yield the 2-methyloctahydroanthracene22. The structures of the compounds were proved by¹H and¹³C NMR spectroscopy, making use of NOE, DEPT, and CH-COSY techniques.

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Synthese und räumliche Struktur von mit drei- bis sechsgliedrigen gesättigten Homocyclen oder Norbornan kondensierten 3(2H)-Pyridazinonen und 1,2-Oxazin-6-onen

Zusammenfassung Die Reaktion voncis-2-(4-methylbenzoyl)-cyclopropan-(1) und-cyclobutancarbonsäuren (2), der stereoisomeren cyclohexyl-Homologen (3 und4) und von di-endo-3-(4-methylbenzoyl)-bicyclo[2.2.1]heptan-2-carbonsäure (5) mit Hydrazinen ergibt die cycloalkankondensierten 3(2H)-Pyridazinone6–9 und das methylenüberbrückte di-endo-Derivat10. Die Verbindungen1 und3–5 wurden mit Hydroxylamin zu den cycloalkan- und norbornankondensierten 1,2-Oxazin-6-onen11–14 umgesetzt.3–6 reagierten zumtrans-Hexahydroanthron17a und seinem methylenüberbrückten Analogen24. Die teilweise gesättigten Anthrone wurden auch aus den stereoisomeren Hexahydro-1(3H)-isobenzofuranonen20 und21 hergestellt (16b und17b), wobei der Methylsubstituent jedoch in Position 6 lokalisiert ist. Reduktion von16b ergab das 2-Methyloctahydroanthracen22. Die Strukturen der Verbindungen wurden durch NMR-Spektroskopie abgesichert (¹H,¹³C, DEPT, CH-COSY, NOE).

     

离子液体中NaHSO4催化芳香醛与1,3-环己二酮的缩合反应

以NaHSO₄为催化剂, 在离子液体1-丁基-3-甲基咪唑四氟硼酸盐([bmim]BF₄)介质中, 由芳香醛与1,3-环己二酮衍生物制备了9-芳基-2,3,4,5,6,7-六氢-2H-氧杂蒽-1,8-二酮衍生物. 在沸水浴中反应1～2 h, 产率达81.2%～93.0%. 该方法反应时间短, 产率高, 催化剂价廉易得, 而且对环境友好.     

Hexafluoroacetone as Protecting and Activating Reagent. Glycosylated Malic, Citramalic, and Thiomalic Acid Derivatives, New Glycosylated Building Blocks for Drug Design [1]

Summary. Glycosylated -hydroxy and -mercapto acids have been synthesized starting from malic/citramalic/thiomalic acid and Ac₄--D-Glc-NH₂/Bzl₄--D-Glc-NH₂ using hexafluoroacetone as protecting and activating reagent.Dedicated to Prof. Dr. Horst Wilde on the occasion of his 65^th birthday     

Research and application of inorganic selective sorbents at Mayak PA

This work has been performed in order to identify selective inorganic sorbents for caesium and strontium. Thin-layer sorbents with nickel ferrocyanide embedded in an inert matrix were found to be the best for caesium. Sorbents including non-stoichiometric manganese dioxide were selected for strontium. Bench tests have been carried out on the purification of desalted water of SNF storage-pool from ¹³⁷Cs, and on the purification of contaminated natural water from ⁹⁰Sr. The facility for synthesizing the ferrocyanide sorbent with the registered mark ‘Seleks-CFN’ has been brought into operation. The sorbent ISM-S seems promising for ⁹⁰Sr decontamination. To cite this article: M.V. Logunov et al., C. R. Chimie 7 (2004).

Résumé

Recherches et applications sur l’utilisation de sorbants spécifiques à Mayak. Des sorbants sélectifs du césium et du strontium ont été identifiés. Pour le césium, le meilleur s’avère être le ferrocyanure de nickel, s’il est utilisé sous forme de couche mince. Pour le strontium, on a sélectionné des composés non stœchiométriques de dioxyde de manganèse. On a mené des tests visant à épurer en césium l’eau des piscines d’entreposage des combustibles nucléaires usagés, et en strontium des eaux contaminées. Une installation industrielle permettant de préparer le sorbant à base de ferrocyanure de marque « Seleks-CFN » a été réalisée. Le sorbant ISM-S semble prometteur pour la décontamination en strontium. Pour citer cet article : M.V. Logunov et al., C. R. Chimie 7 (2004).     

双胍辛醋酸盐杀菌剂及其两种中间体的合成与生物活性

O-methylisourea acetate was synthesized by two procedures from the main raw materials including carbamide, dimethyl sulfate, acetic acid and concentrated sulfuric acid. Its content reaches 98 % and the total yield attains to 70%. 1, 17-Diamino-9-azaheptadecane was first synthesized by two procedures using sebcic acid, 1,8-octanediamine, sodium azide and concentrated sulfuric acid as the main raw materials. Its content reaches 98% and the total yield is 65%. The structure of both were confirmed by FT-IR, ^1H NMR and their available analysis method was established. Fungicide bis-(8-guanidino-octyl )amine acetate was synthesized from these two intermediates and its structure was confirmed by FT-IR and ^1HNMR. Fungicidal activity test showed that it is a kind of broad-spectrum fungicide with notably effect.     

Condensation of 1-carbamoylmethyl-2,3,3-trimethyl-3H-indolium chloride with aromatic aldehydes

The reaction of 1-carbamoylmethyl-2,3,3-trimethyl-3H-indolium chloride with various aromatic aldehydes in acetic acid and the subsequent workup of the intermediate styrylic derivatives with strong bases yielded 9a-(2-arylethenyl)-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one derivatives. Condensation of the mentioned salt with salicylaldehyde in acidic or basic medium afforded the derivative of l-carbamoylmethylspiro[benzopyran-2,2-indole]. Alkylation of the latter compound with benzyl chloride in the presence of potassium hydroxide gave 9a-[2-(2-benzyloxyphenyl)ethenyl]-1,2,3,9a-tetrahydro-9H-imidazo[1,2-a]indol-2-one.Department of Organic Chemistry, Kaunas University of Technology, LT-3028 Kaunas, Lithuania Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 761–769, June, 2000.     

STUDY ON APPLICATION OF POTASSIUM TITANATE WHISKER MATERIALS IN PREPARATION OF PHOTOCATALYST

The K2Ti4O9 whiskers were chosen for the catalyst carrier, TiO2/potassium titanate photocatalyst was prepared by Sol-gel method The product was characterated by X-ray diffraction and SEM. EDS shows that, the main peck included Ti, O, and K in potassium titanate whisker. The main peak of K disappeared and the peaks of Ti, O stayed after whisker was covered It directed that the surface of sample was covered by TiO2. XRD shows that diffraction peak appeared, which was corresponded to the peak of anatase TiO2. In the reaction device of photochemistry, using middle-pressure mercury lamp as illumination, rhodamine B as simulant pollutant, the photocatalytic performance of TiO2/potassium titanate was studied. Under the same conditions, the lower pH, the larger illuminance, the higher temperature, the greater aeration quantum and the lower initial concentration of rhodamine B, the higher decoloration rate was got. Under our experiment conditions： pH 6, the illuminance of 250W, the temperature of 313K, and the aeration quantum of 2.0L/min. When the concentration of rhodamine B was 8mg/L The photocatalyst of TiO2/potassium titanate was 0.01g/L. The decoloration rate of TiO2/potassium titanate dealt with the rhodamine B reach over 95% in 160min, and compare with TiO2, the decoloration rate of rhodamine B was improved 0.50-1.91 multiple. TiO2/potassium titanate can be used to treatment of dye wastewater.     

Synthetic studies of erythromycin derivatives: 6-O-methylation of (9S)-12,21-anhydro-9-dihydroerythromycin A derivatives

Synthetic studies on methylation of erythromycin derivatives were conducted. Methylation of 6 resulted in the formation of the C-3′ quaternary ammonium salts with a rate faster than 6-O-methylation. In dipolar aprotic solvent and under strong base conditions, 6-O-methylation, C-3′ quaternary ammonium salts formation and 2-C-methylation proceeded simultaneously to yield a mixture of three different products 7, 8 and 9. The quaternary ammonium salts were converted back to the corresponding tertiary amines 2, 10 and starting material 6 by employing sodium 4-pyridinethiolate as a N-demethylation reagent. The 6-O-methylation was eventually achieved in a good yield when a carbobenzyloxy (Cbz) group was utilized to protect the C-3′-dimethylamino group of 4. In this report, we will discuss the details of different reaction courses in the methylation of (9S)-12, 21-anhydro-9-dihydroerythromycin A derivatives.     

有机三膦酸锌配合物的合成与晶体结构

合成了一种新型的有机三膦酸配体H6aptp[1-氨基-丙基-1,1,3-三膦酸],并在水热条件下合成了它的锌配合物[Zn(H4aptp)(2,2′-bipy)(H2O)].2H2O.用红外、质谱、元素分析、热重分析等手段对其进行了表征并解析了它的单晶结构.实验结果表明:配合物属三斜晶系,空间群为P,ī晶胞参数为a=0.66814(5)nm,b=1.00929(7)nm,c=1.5438(11)nm,α=81.544(10)°,β=79.066(10)°,γ=82.278(10)°,Z=2,V=1.00495(13)nm3,配合物在空间上以一维链状方式排列.