Study of nitrogen- and sulfur-containing heterocycles. 54. Properties and conversions of pyrimido[4,5-<Emphasis Type="Italic">b</Emphasis>]-1,4-benzothiazepines. Synthesis of a novel heterocyclic system: Pyrimido[5,4-<Emphasis Type="Italic">c</Emphasis>]isoquinoline

We have studied some properties and conversions of pyrimido[4,5-b]-1,4-benzothiazepines: reduction, oxidation, reactions with nucleophilic reagents (methanol, hydrazine, hydroxylamine, o-methylhydroxylamine, and thiosemicarbazide). We have synthesized derivatives of a novel heterocyclic system: pyrimido[5,4-c]isoquinoline.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1863–1872, December, 2004.For Communication 53, see [1].     

Preparation of novel analgesics via diastereoselective nucleophilic addition to 1-dimethylamino-2-methylpentan-3-one

The diastereoselective synthesis of naphthyl amino alcohols via nucleophilic addition to racemic 1-dimethylamino-2-methylpentan-3-one was studied. The use of the appropriate experimental conditions allowed the synthesis of both diastereoisomers. The relative configurations were established via NOESY experiments.     

Transition metal 1,2-bidentate thiolates as building blocks and their construction into cluster complexes

Simple fragments of transition metal 1,2-bidentate thiolates, the so-called building blocks of the general compositions ML₃, ML₂, ML, M(O)L₂, ML₂L, MLL, etc. have been proposed to constitute the di-, tri- and tetranuclear complexes concerned in this review. Structureal regularities and characteristics have been discussed and summarized according to the thiolato ligands edt and pdt, bdt and tdt, mp, and mpo, and mpp, respectively.Abbreviations H₂mpo o-mercaptophenol - Hmpo 2-mercaptopyridine-N-oxide - R₂dtc N,N-dialkyldithiocarbamate - Haet 2-aminoethanethiol - H₂bdt o-benzenedithiol - H₂pdt 1,2-propanedithiol - H₂tdt toluene-3,4-dithiol - Hmpp-mppH bis-(3-hydroxy-2-pyridyl)disulfide - Hmp-mpH bis-(2-oxyphenyl)disulfide - H₂edt 1,2-ethanedithiol - dppe 1,2-bis(diphenylphosphino)ethane - H₂tedt 3,4,5,6-tetrachlorobenzene-1,2-dithiol - H₂tpdt 3-thiapentane-1,5-dithiol - H₂mnt maleonitriledithiol - Him imidazole - Bz benzyl - py pyridine     

Synthesis and structural characterization of [Au2Pd14(μ3-CO)7(μ2-CO)2(PMe3)11](PF6)2—An icosahedrally-based high nuclearity mixed metal cluster

[Au₂Pd₁₄(₃-CO)₇(₂-CO)₂(PMe₃)₁₁](PF₆)₂ has been synthesized from [Pd₈(CO)₈(PMe₃)₇] and AuCl(PCy₃) in the presence of TIPF₆. It has been characterised on the basis of mass spectrometry, infrared and NMR spectroscopy, and a single crystal X-ray diffraction study. The structure is based on a palladium-centered Au₂Pd₁₁ icosahedron which shares an edge with a Pd₅ trigonal bipyramid.This paper is dedicated to Larry Dahl on his 65th Birthday—his enthusiasm and achievements in cluster chemistry have inspired us all for more than 30 years.     

β—芳氧基丙酸衍生物的合成及生物活性

合成了β－芳氧基丙酸芳酯及β－芳氧基丙酰芳胺等１７种化合物，经ＩＲ，ＵＶ，ＨＮＭＲ和元素分析确定了它们的结构，并对它们的生物活性进行了初步考察。     

Rh-TPPTS/CTAB-MMT催化剂的制备及其催化长链烯烃氢甲酰化反应性能研究

通过浸渍法将水溶性铑膦配合物(Rh-TPPTS)负载到由十六烷基三甲基溴化铵(CTAB)修饰的蒙脱土(MMT)上,制备出Rh-TPPTS/CTAB-MMT负载型催化剂.采用XRD,FTIR,TG,BET,31P CP-MAS NMR和分散性实验对催化剂进行了表征.结果表明:水溶性铑膦配合物成功地负载到有机MMT上,并且该催化剂在有机溶剂中具有很好的分散性.该催化剂对于1-癸烯的氢甲酰化反应具有好的催化活性.在100℃、4 MPa、甲苯为溶剂的条件下,催化1-癸烯氢甲酰化可获得93.0%的转化率,95.8%的醛的选择性,2.1的正异比,137 h-1的TOF值.并对不同链长烯烃底物进行了考察.随着烯烃碳链的增加,醛的选择性下降,但是正异比有所增加.     

Reversible grafting of α-naphthylmethyl radicals to epitaxial graphene

The Kolbe electrochemical oxidation strategy has been utilized to achieve an efficient quasireversible electrochemical grafting of the α-naphthylmethyl functional group to graphene. The method facilitates reversible bandgap engineering in graphene and preparation of electrochemically erasable organic dielectric films. The picture shows Raman D-band maps of both systems.     

Darstellung und Molekülstrukturen von oligofunktionalen Dirheniumcarbonylderivaten aus Dirheniumnonacarbonylphosphan

Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re₂(CO)₉NCCH₃ was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re₂(CO)₉PH₃, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re₂(CO)₉PH₃ led to the new bi- and trinuclear complexes Re₂(μ-H)(μ₃-PHRe(CO)₅)(CO)₈, Re₂(μ-PH₂)₂(CO)₈ and Re₂(μ-H) · (μ-PH₂)(CO)₈, which were characterized by IR-, ¹H- and ³¹P-NMR spectroscopy. The structures of ax-Re₂(CO)₉PH₃, Re₂(μ-H)(μ₃-PHRe(CO)₅)(CO)₈ and Re₂(μ-PH₂)₂(CO)₈ were confirmed by single-crystal X-ray analysis. ax-Re₂(CO)₉PH₃ has a very short Re? P bond length of 228(2) pm.