Das erste Oxid vom Formeltyp K5[MO4]: K5[TIO4] [1]

The First Oxide with the Formula Type K₅[MO₄]: K₅[TlO₄] Light yellow powder and pale yellow transparent single crystals of K₅[TlO₄] were newly prepared from mixtures of binary oxides (K₂O/Tl₂O₃) preheated and levigated several times [closed Ag-cylinder, 580°C, 24 h and 600°C, 20 d]. Space group Pbca with a = 1170.4(3), b = 686.1(1), c = 2079.2(5) pm, Z = 8 [four-circle-diffraktometer data, 997 I₀(hkl), R = 7.87%, R_w = 5.63%, MoKα] (parameter s. text). The crystal structure belongs to the Na₅[GaO₄] type. Structural aspects, ECoN and MAPLE are discussed.     

Organic clays. Synthesis and structure of Na5[calix[4] arene sulfonate] · 12 H2O,K5[calix[4]arene sulfonate]·8 H2O,Rb5[calix[4]arene sulfonate]·5 H2O,and Cs5[calix[4] arene sulfonate] ·4 H2O

The title calixarenes all exist in the solid state as bilayers of anionic calixarenes in the cone configuration. These layers alternate with inorganic regions which contain the cations and the water molecules. The overall structures bear a close resemblance to those found for clay minerals. The sodium salt crystallizes in the triclinic space groupP witha = 10.998(6),b = 13.582(5),c = 14.472(5) Å, = 74.01(3), = 89.09(4), = 86.50(4)°, andZ = 2 forD _calc = 1.72 g cm^–3. Refinement based on 4727 observed reflections led to a conventionalR = 0.050. The potassium salt crystallizes in the triclinic space groupP witha = 11.815(9),b = 13.636(6),c = 14.040(9) Å, = 100.24(5), = 111.86(9), = 95,14(9)°, andZ = 2 forD _calc = 1.77 g cm^–3. Refinement based on 2977 observed reflections led toR = 0.15. The rubidium and cesium salts are isostructural and crystallize in the monoclinic space groupP2₁/n with parameters for Rb[Cs]a = 11.603(5) [11.704(3)],b = 28.607(8) [29.747(9)],c = 12.512(5) [12.604(4)] Å, = 91.70(4) [91.63(2)°], andZ = 4 forD _calc = 2.01 [2.24] g cm^–3. Refinement based on 1750 [4257] observed reflections led toR = 0.108 [0.075]. Disorder of the cations was observed for the rubidium and cesium salts. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82074 (95 pages).     

Calix[4]- and calix[5]arene-based multicavity macrocycles

Synthesis and single-crystal X-ray structures of mixed triple and double calixarenes 6 and 7, obtained from the base-catalyzed condensation of calix[5]arene 1 with cone pertosylated calix[4]arene 2, are reported. VT-NMR studies on 7 are consistent with a molecular motion arising from the anti-gauche conformational interconversion of its ethylene linkages.     

Zur Kenntnis der Na5[GaO4]-Verwandtschaft: KNa4[GaO4] und CsK4[GaO4]

About the Na₅[GaO₄]-Relationship: KNa₄[GaO₄] and CsK₄[GaO₄] KNa₄[GaO₄] was newly prepared from binary oxides (powders) and also from KGaO₂/Na₂O/K₂O (colourless columnar single crystals) in a closed Ag-cylinder at 600 and 650°C. Space group Pbca with a = 1046.1(2), b = 596.3(1), c = 1871.1(3) pm, Z = 8 [Four-circle-diffractometer data, 1138 I₀(hkl), MoKα, R = 8.29, R_w = 6.76%, anisotropic refinement] (Parameter s. text). Colourless cubic single crystals of hitherto unknown CsK₄[GaO₄] are formed by reaction of K₂O, CsGaO₂, and Cs₂O (surplus) in a closed Au-tube at 580°C. Space group Pbca with a = 1154.7, b = 667.7, c = 2096.6 pm, Z = 8 [Four-circle-diffractometer data, 1798 I₀(hkl), MoKα, R = 7.62, R_w = 7.68%, anisotropic refinement] (Parameter s. text). Both crystal structures belong to the Na₅[GaO₄] type. Structural aspects, ECoN, and MAPLE of KNa₄[GaO₄] and CsK₄[GaO₄] in relation with Na₅[GaO₄] are discussed.     

杯[4]单硫(硒)杂冠-5的合成及其对金属离子的识别性能研究

从简单无机硫、硒化合物直接合成冠醚环上含硫、硒杂原子的杯[4]单硫杂冠-5及杯[4]单硒杂冠-5;化合物的结构经¹HNMR、MS及元素分析确证.并研究了它们对Na⁺,K⁺,NH⁴⁺,Co²⁺,Ni²⁺,Ag⁺及Hg²⁺的两相萃取性能,发现其对Ag⁺、Hg²⁺有较好的识别能力.     

Synthesis and Characterization of Na5[VO4][O] and Na4[VO4][OH]

Na₅[VO₄][O] and Na₄[VO₄][OH] were obtained from reactions of V₂O₅ with Na₂O and additional NaOH in the latter case, respectively, at 600‐700 °C in sealed Ag containers under Ar atmosphere. The crystal structures have been determined from X‐ray single crystal data. The structures contain isolated [VO₄]^3? complexes and non‐coordinating oxide and hydroxide anions, respectively. Raman and infrared data is compared for both compounds and hydrogen bonding is discussed for Na₄[VO₄][OH].     

The syntheses of 4b,5a-dihydrodibenz[3,4:5,6]anthra[1,2-b]oxirene and 4b,5a-dihydro-5H-dibenz[3,4:5,6]anthra[1,2-b]azirine

The syntheses of the K-oxide and K-imine derivatives of dibenz[a,j]anthracene ( 1 ) are described. The parent hydrocarbon 1 that was obtained as a side product in the Elbs pyrolysis of (2-methyl-1-naphthyl)-1′-naphthylmethanone ( 10 ) was oxidized to 3-(2-formylphenyl)-3-phenanthrenecarboxaldehyde ( 3 ). Treatment of the dialdehyde with tris(dimethylamino)phosphine gave 4b,5a-dihydrodibenz[3,4:5,6]anthra[1,2-b]oxirene ( 4 ). Reaction of the oxirane with sodium azide followed by triethyl phosphite cyclization of the mixture of trans azido-alcohols so formed, yielded mainly 4b,5a-dihydrodibenz[3,4:5,6]anthra[1,2-b]azirine ( 5 ).     

Rhodium N-heterocyclic carbene-catalyzed [4 + 2] and [5 + 2] cycloaddition reactions

[reactions: see text] A rhodium complex of N-heterocyclic carbene (NHC) has been developed for intra- and intermolecular [4 + 2] and intramolecular [5 + 2] cycloaddition reactions. This is the first use of a transition-metal NHC complex in a Diels-Alder-type reaction. For the intramolecular [4 + 2] cycloaddition reactions, all the dienynes studied were converted to their corresponding cycloadducts in 91-99% yields within 10 min. Moreover, up to 1900 turnovers have been obtained for the intramolecular [4 + 2] cycloaddition at 15-20 degrees C. For the intermolecular [4 + 2] cycloadditions, high yields (71-99%) of the corresponding cycloaddition products were obtained. The reaction time and yield were highly dependent upon the diene and the dienophile. For the intramolecular [5 + 2] cycloaddition reactions, all the alkyne vinylcyclopropanes studied were converted to their corresponding cycloadducts in 91-98% yields within 10 min. However, the catalytic system was not effective for an intermolecular [5 + 2] cycloaddition reaction.     

Synthesis and structure of ammonium phenylpenta-fluoroantimonate 2NH4[C6H5SbF5]·NH4[HF2]

M. V. Lomonosov Moscow State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 5, pp. 138–140, September–October, 1990.     

Cation recognition by new diester- and diamide-calix[4]arenediquinones and a diamide-benzo-15-crown-5-calix[4]arene

The synthesis, metal, ammonium and alkyl ammonium cation coordination chemistry and electrochemical recognition studies of new diester-and diamide-calix[4]arenediquinone receptors are described. In addition the synthesis and coordination properties of a novel diamide benzo-15-crown-5-calix[4]arene molecule is reported.This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

Synthesis of 2-mercaptothieno[3,2-d]- and 2-mercaptobenzo[4, 5]thieno[2,3-d]thiazoles

2-Mercaptothieno[3,2-d]- and 2-mercaptobenzo[4, 5]thieno[2,3-d]thiazoles were synthesized by reduction of bis(3,3′-nitro-2,2′-thienyl) and bis(2,2′-nitrobenzo[b]thien-3,3′-yl) disulfides, respectively, with sodium hydrosulfite or sodium sulfide in the presence of carbon disulfide.     

5-氢-1,4,6,9-四氧-5-膦螺环[4.4]壬烷的制备及其硅烷基化反应

5-氢-1,4,6,9-四氧-5-膦螺环[4.4]壬烷2是合成有机磷阻燃剂的重要原料.其合成方法虽有一些报道,但尚未见2-氯-1,3,2-二氧膦杂环戊烷1与乙二醇反应的合成路线.我们用1、乙二醇及三乙胺以等摩尔比反应,发现2的收率很低,主要得到环状二亚磷酸酯3,将3再与乙二醇反应,很容易转化成2,反应式如下: