Interaction of Methyl 5,6-Dialkyl-2-amino-3-cyanopyridine-4-carboxylates with Primary Amines

An unusual direction has been found for the interaction of alkyl 5,6-dialkyl-2-amino-3-cyanopyridine-4-carboxylates with primary amines leading to the formation of 2,6,7-trialkyl-4-amino-2,3-dihydro-1H-pyrrolo[3,4-c]pyridine-1,3-diones.     

Transformations ofmyo-inositol hexa-O-nitrate under the action of amines

Reactions ofmyo-inositiol hexa-O-nitrate with ammonia and primary amines yield tetrahydroxy-1,4-benzoquinone derivatives,viz., its tetraammonium salt and its diimines, respectively. Reactions with secondary and tertiary amines give salts of rhodizonic acid, which are converted into salts of croconic acid under certain conditions. The reactions with secondary amines involve intermediate formation of radical species, which were dectected by ESR spectroscopy. A scheme for the chemical transformations ofmyo-inositol hexa-O-nitrate under the action of amines was proposed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2962–2967, December, 1996.     

Crystal Structures of 1,5,9,18,22,26-Hexaaza[11.11]-p-cyclophane Adducts; Two-dimensional Supramolecular Networks

Two newly identified supramolecular structures arise from self-assembly of the macrocyclic 1,5,9,18,22,26- hexaaza[11.11]-p-cyclophane salts with o-nitrophenol (C₂₈H₅₀N₆)⁴⁺·4(C₆H₄NO₂O)⁻ (1) and with HCl (C₂₈H₅₂N₆)⁶⁺·6Cl^-·4H₂O (2). In both cases two-dimensional supramolecular sheets are formed.     

Simple route to secondary amides of phosphorylacetic acids and their use for extraction and sorption of actinides from nitric acid solutions

An efficient method for the synthesis of secondary alkylamides of phosphorylacetic acids (APA) was proposed. The method involves amidation of ethyl phosphorylacetates with primary aliphatic amines. The scope of reaction was determined. Reactions with ethylenediamine and 1,4-diaminobutane yield the corresponding bisamides; in the case of 1,3-diaminopropane, N-(3-aminopropyl)diphenylphosphorylacetamide or N,N-propylenebis(diphenylphosphorylacetamide) was obtained, depending on the reaction conditions. The extraction of americium(III) complexes and the sorption of uranium(VI) by sorbents with physically sorbed APA from nitric acid solutions were studied. There is no correlation between the partition coefficient of americium(III) and the structure of APA; in the sorption of uranium(VI), the degree of extraction depends on the complexone structure.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2394–2402, November, 2004.     

Asymmetric synthesis of 1-substituted-1-(pyridin-2-yl)methylamines by diastereoselective reduction of enantiopure N-p-toluenesulfinyl ketimines

Reduction of enantiopure N-p-toluenesulfinyl ketimines derived from 2-pyridyl ketones affords N-p-toluenesulfinyl amines with good yields and diastereoselectivities.     

胺类化合物气相色谱保留指数与结构的相关性研究

应用Ａｍ指数和引力指数Ｇ１对在３种体系下的胺类化合物的气相色谱保留指数和结构进行了相关性研究,并运用最佳子变量集算法和人工神经网法进行了计算分析,在非极性固定相ＯＶ－１０１和极性固定相ＯＶ－２２５和ＮＧＡ下均获得了比较好的相关模型。     

Polysulfonylamine. XLI. Ein Silber(I)-Hydrat ungewöhnlicher Zusammensetzung: Röntgenstrukturanalytische und thermochemische Charakterisierung von Tetrakis(dimesylamido)aquatetrasilber(I) [Ag4(N(SO2CH3)2}4(H2O)]

Polysulfonyl Amines. XLI. A Silver(I) Hydrate with an Unusual Composition: Characterization of Tetrakis(dimesylamido)aquatetrasilver(I) [Ag₄(N)SO₂CH₃)₂}₄(H₂O)] by X-Ray Diffraction and Thermal Analysis The title compound is obtained by crystallizing AgN(SO₂CH₃)₂ from water at room temperature. Crystallographic data (at ?95°C): Triclinic space group P1 , a = 864.6(4), b = 1 211.2(5), c = 1 399.1(5) pm, α = 90.97(3), β = 90.90(3), γ = 98.25(4)°, V = 1.4496 nm³, Z = 2, D_x = 2.608 Mg m^?3. The four independent silver atoms and the water molecule form zigzag chains Ag(1)-Ag(2)-(μ-H₂O)-Ag(3) …? Ag(4) …? Ag(1′) with distances Ag(1)-Ag(2) 309.7, Ag(2)-O(w) 241.8, O(w)-Ag(3) 241.4, Ag(3) …? Ag(4) 342.9, Ag(4) …? Ag(1′) 361.4 pm. The catenated silver atoms are further connected by the dimesylamide anions acting as tridentate bridging (α-O, N, ω-O)-ligands. The resulting strands are interconnected into layers through one O(S)-Ag′ contact (247 pm) and one hydrogen bond O(w)-H(l) …? O′(S) per repeating unit. Between the layers, a weak O(S) …? Ag″ interaction (271 ptn) and a hydrogen bond O(w)-H(2) …? O(S) per repeating unit are observed. The silver atoms Ag(l) to Ag(4) display the coordination numbers 5 [NO,Ag(2), distorted trigonal bipyramid], 5[NO₂,O(w)Ag(I), distorted trigonal bipyramid], 5[O₄,O(w), trigonal bipyramid], and 2 + 1 (N₂, li-near; plus a secondary Ag …? 0 contact). The dehydration of the title compound and a solid-solid phase transformation in anhydrous AgN(SO₂CH₃)₂, were quantitatively investigated by thermoconductometry and time- and temperature-resolved X-ray diffractometry (TXRD).     

A novel synthesis of substituted quinolines using ring-closing metathesis (RCM): its application to the synthesis of key intermediates for anti-malarial agents

A method for synthesizing substituted quinolines using ruthenium-catalyzed ring-closing metathesis as a key step has been developed. Substituted 1,2-dihydroquinolines, 4-silyloxy-1,2-dihydroquinoline and 4-methoxy-1,2-dihydroquinoline, were successfully synthesized in excellent yields via ene-ene metathesis and silyl or alkyl enol ether-ene metathesis, respectively. The synthetic intermediates of the antimalarial agents quinine, chloroquine, and PPMP-quinine hybrid were efficiently synthesized by this methodology.     

Extraction of uranium(IV) and uranium(VI) by primary and tertiary-amines from sulphate solutions

In developing a method for possible low level isotopic enrichment, which uses to advantage the equilibrium isotope effect observed during U(1V)-U(VI) electron exchange reaction in sulphate solutions, details of a solvent extraction process involving high concentration of a mixture of U(IV) and U(VI) and at low acid concentrations, are described. The extraction behaviour of uranium under these conditions is discussed. During the extraction with amines, U(IV) tended to get oxidised in sulphate solutions.     

Enantiomeric Separation of Adrenergic Amines in Citrus Species, Related Genera and Dietary Supplements by Capillary Electrophoresis

Citrus aurantium L. (Rutaceae) fruit extracts have recently been used for weight loss. Among the adrenergic amines the most important active constituent is the sympathomimetic compound synephrine and commercially available extracts are standardized for their content of this active principle. A capillary electrophoresis method was developed for the quantitative and qualitative determination of d-synephrine, l-synephrine, d-octopamine, l-octopamine, tyramine, n-methyl tyramine and hordenine. The electrophoretic separation was performed using a 75 cm × 50 µm ID (66.5 cm effective length) fused silica capillary. The samples were injected by pressure for 5s at 50 mbar and the running voltage was 30 kV at the injector end of the capillary. The method developed was successively applied to the determination of the adrenergic amines in dietary supplements, in various Citrus species including Citrus aurantium, jams and juices. Synephrine was the main component and present in the levels from 0.02–0.17% in various Citrus species and 0.42–69.28 mg in dietary supplements claiming to contain Citrus aurantium. Parameters affecting the resolution between (+) and (−)-enantiomers, such as pH, cyclodextrin concentration, temperature, organic modifier, buffer concentration and capillary dimensions were reported.