1,2-Dialkoxyacenaphthylenes and 2,3,11,12-bis-(1,2-acenaphtho)-[18]crown-6

A general synthesis of 1,2-dialkoxyacenaphthylenes by dehydrogenation of the corresponding acenaphthene derivatives with high potential quinones is described. The new crown ether, 2,3,11,12-bis(1,2-acenaphtho)-[18]crown-6, 1, is obtained by this route. The surprisingly poor complexing ability of 1 is ascribed to electronic and geometrical effects of the acenaphthylene rings as shown by spectroscopic and voltammetric data and the crystal structure of the free ligand 1.     

Crystal structures and solution conformations of the meso-forms of 2,3,11,12-Tetraphenyl-[18]crown-6

The X-ray crystal stuctures of the achiral cis-anti-cis and trans-syn-trans diastereoisomers of 2,3,11,12-tetraphenyl-[18]-crown-6 and their sodium iodide 1:1 complexes are presented. In the free ligands, the vicinal phenyl groups assume a diaxial- antiperiplanar orientation in the cis-anti-cis isomer and a diequatorial-synclinal one in the trans-syn-trans isomer. The vicinal coupling constants of the benzylic protons in the diphenylethanediyl groups in the three meso-forms, derived from ¹³C satellites, suggest similar conformations in the solid state and in deuteriotrichloromethane solution. Conformational changes of the crown ethers from the free ligand to their complexes are discussed in the context of previously determined complex association constants.     

Supramolecular rotor: adamantylammonium([18]crown-6) in [Ni(dmit)2]- salt

Adamantylammonium (ADNH3+) was complexed with [18]crown-6, forming a supramolecular cation of (ADNH3+)([18]crown6), which was introduced into a [Ni(dmit)2]- salt as a supramolecular rotor. The cation layers were alternately arranged with [Ni(dmit)2]- layers in the crystal, in which the molecular rotation of (ADNH3+)([18]crown-6) was confirmed from the temperature-dependent solid-state 1H NMR.     

Estimation of Li+, K+ and Ca2+ Complexation with [12] crown-4, [15] crown-5 and [18] crown-6 Using a Na+ ISE in Dioxane-Water, Part IV*

 The (1:1) Na⁺ equilibrium constants, Ke1, of macrocyclic ethers of [12]crown-4, [12]crown-5 and [18]crown-6 were determined with a Na⁺ ISE in the presence of a second cation e.g. Li⁺, K⁺ and Ca²⁺ in dioxane/water (50/50). We estimated the (1:1) equilibrium constants, K e2 of the macrocyclic ethers with Li⁺, K⁺ and Ca²⁺ by this way. The binding selectivity of a macrocyclic ether between two cations was estimated in the same binary solvent mixture where the water hydration role is diminished. Results showed clearly the effect of macrocyclic size and cation radii in a solution. Received October 27, 1998. Revision March 22, 1999.     

BOTPPI, a new Wittig salt for the synthesis of 12-(S)-hydroxy-eicosatetraenoic acid [12-(S)-HETE]

An efficient route to (Z)-(8-benzyloxy-8-oxooct-3-en-1-yl)triphenylphosphonium iodide, or BOTPPI, is disclosed, complete with full experimental details, NMR spectra, and HRMS data. BOTPPI serves as a surrogate for (Z)-(8-methoxy-8-oxooct-3-en-1-yl)triphenylphosphonium iodide, or MOTPPI, a Wittig salt previously used in two 12-HETE syntheses. BOTPPI has the advantage over MOTPPI of being derived from a sequence for which every intermediate is UV-active and amenable to large-scale chromatographic purification. A formal asymmetric total synthesis of 12-(S)-HETE is also reported, involving a stereoselective phase-transfer catalyzed (PTC) alkylation in its key step.     

Synthesis of (+)-2R,3R,11R,12R- and (−)-2S,3S,11S,12S-tetraphenyl-18-crown-6

The synthesis of the title crown ethers starting from optically active hydrobenzoins is described. R(+)-1,in CDCl₃ ,preferentially extracts R(+)-phenylglycine methyl ester hydroperchlorate from an aqueous solution of the racemate with a chiral recognition factor of 1.5 as shown by nmr measurements.     

61-甲基-61-[12-(18-N-四氯邻苯二甲酰亚氨基)脱氢枞胺]-1,2-亚甲基富勒烯[60]的合成

以脱氢枞胺为原料,经氨基酰化、12位乙酰化、与对甲苯磺酰肼形成对甲苯磺酰腙衍生物,再通过卡宾中间体与C60进行[2+1]环加成反应合成了C60-脱氢枞胺衍生物。目标化合物经IR,UV-Vis,1H NMR,13C NMR,MALDI-TOF MS表征,所得化合物为[6,6]闭环结构C60加成产物。     

Supramolecular cations of the m-fluoroanilinium(dibenzo[18]crown-6) in ferromagnetic salt

A supramolecular cation of (m-FAni(+))(DB[18]crown-6), where m-FAni(+) and DB[18]crown-6 denote m-fluoroanilinium(+) and dibenzo[18]crown-6, respectively, which is the polar unit rotating in the ferroelectric crystal of (m-FAni(+))(DB[18]crown-6)[Ni(dmit)(2)](-), was introduced into a ferromagnetic [MnCr(oxalate)(3)](-) salt as the counter cation. The crystal structure of (m-FAni(+))(DB[18]crown-6)[MnCr(oxalate)(3)](-)(CH(3)OH)(CH(3)CN) (1) is constructed from alternating layers of a two-dimensional honeycomb layer of [MnCr(oxalate)(3)](-) and (m-FAni(+))(DB[18]crown-6) supramolecular cations. The anionic layer is composed of Mn(II) and Cr(III) ions with S = 5/2 and S = 3/2 spins, respectively, bridged by the oxalate anions, which show ferromagnetic ordering at 5.5 K. The supramolecular structure is formed through the formation of hydrogen bonds between the ammonium hydrogen atoms of the m-FAni(+) cations and the oxygen atoms of the DB[18]crown-6 cavity. No orientational disorder of the fluorine atoms was observed in our X-ray structural analysis, suggesting that a two-fold flip-flop motion of the m-FAni(+) cations does not occur in the salt. The rotational freedom of the m-FAni(+) cations in the salt is restricted by the steric hindrance from neighbouring DB[18]crown-6 molecules. A design strategy for the rotation in a salt is discussed, based on the volume that the supramolecular cations occupy in the unit cell.     

Synthesen und Kristallstrukturen der chalkogenidoverbrückten Nickelclusterverbindungen [Ni5Se4Cl2(PPhEt2)6], [Ni12Se12(PnPr3)6] und [Ni18S18(PiPr3)6]

Syntheses and Crystal Structures of Chalcogenido‐bridged Nickel Cluster Compounds [Ni₅Se₄Cl₂(PPhEt₂)₆], [Ni₁₂Se₁₂(PⁿPr₃)₆], and [Ni₁₈S₁₈(PⁱPr₃)₆] The reaction of (R)ESiMe₃ (R = SiMe₃, Mes = C₉H₁₁; E = S, Se) with [NiCl₂(PPhEt₂)₂] and [NiCl₂(PR₃)₂] (R = ⁿPr, ⁱPr) gives new chalcogenido‐bridged nickel cluster compounds [Ni₅Se₄Cl₂(PPhEt₂)₆]·2THF ( 1 ), [Ni₁₂Se₁₂(PⁿPr₃)₆]·2THF ( 2 ), and [Ni₁₈S₁₈(PⁱPr₃)₆]·2THF ( 3 ). The structures of these compounds were determined by single crystal X‐ray structural analyses.     

6-溴-3-[2-(6-溴-2-甲氧基喹啉-3-基)-1,2-二苯乙基]-2-甲氧基喹啉的合成

以6-溴-3-(氯苯基甲基)-2-甲氧基喹啉(2)为起始原料,经过偶合对接反应合成了新型喹啉类抗结核药物TMC-207的衍生物6-溴-3-[2-(6-溴-2-甲氧基喹啉-3-基)-1,2-二苯乙基]-2-甲氧基喹啉,其结构经1H NMR和HR-MS确证.最佳反应条件:2 10 mmol,Et_3N 5 mL,KI 0.17 g,乙腈150 mL,于80 ℃反应6 h,收率73%.     

Magnetism of [Ni(dmit)2] salts with [meso- and (1S, 2S)-diphenyl-1,2-ethanediammonium]([18]crown-6)2 supramolecular cations

Meso- and (1S, 2S)-diphenyl-1,2-ethanediammonium (DPEDA2+) complexed with [18]crown-6 were introduced into [Ni(dmit)2]-based magnetic salts as countercations. The configurational difference of DPEDA2+ modulated the crystal structure and magnetic behavior of the salts. A two-dimensional (2D) Heisenberg antiferromagnetic square lattice was observed in (meso-diphenyl-1,2-ethane diammonium2+)([18]crown-6)2[Ni(dmit)2](-)2, which was the first example of a 2D magnetic lattice in [Ni(dmit)2]- salts.     

Synthesis and structure of the silylated benzene radical anion salts [K([18]crown-6){C6H4(SiMe3)2-1,4}] and [K([18]crown-6)(THF)2][C6H2(SiMe3)4-1,2,4,5]

The crystalline compound [K([18]crown-6){C₆H₄(SiMe₃)₂-1,4}] (1) was prepared by the low-temperature reduction of the para-disilylated benzene with K/[18]crown-6 in toluene followed by recrystallisation from the same solvent. Reduction of 1,2,4,5-tetrasilylated benzene with 2(K/[18]crown-6) in toluene produced a hydrocarbon-insoluble powder identified as the dianionic derivative [K([18]crown-6)]₂[C₆H₂(SiMe₃)₄-1,2,4,5)] (2), which upon crystallisation from THF/Et₂O yielded [K([18]crown-6)(THF)₂][C₆H₂(SiMe₃)₄-1,2,4,5] (3). An X-ray diffraction study revealed that 1 comprised a contact ion pair with the crown-encapsulated K cation η⁵-connected to the planar ring of the substituted benzene radical anion, while 3 contained a well separated cation and anion.