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121.
Structures and Molecular Properties of Charge-Pertubed Molecules. 2, 3-Diphenylquinoxaline Radical Anions in Solution and in Crystals The Na⊕ and K⊕ radical-ion salts of 2, 3-diphenylquinoxaline seem to be (according to a structural database search) among the first ones of N-heterocyclic radical anions in crystals. The one-electron reduction in aprotic 1, 2-dimethoxyethan (DME) solution at metal mirrors and the crystallization under Ar have been preceded by cyclovoltammetric (CV) and ESR/ENDOR measurement. The first electron insertion at ?1.63 V proves to be reversible, whereas the irreversible second step, which is accompanied by an overcrossing of the CV line, can be rationalized by an ‘ECE-DISP’ mechanism via a dianion redox disproportionation. The ENDOR spectrum resolves four 1H couplings and allows to simulate the ESR spectrum including the 14N hyperfine splittings. Both dark-blue single crystals of the radical ion salts $[2,3{\rm - diphenylquinoxaline}^{{.} \ominus} {\rm Met}^ \oplus ({\rm DME})]^.$ show unexpected similarities for Met⊕ = Na⊕, K⊕ despite the 36-pm difference in their ionic radii. The largest structural changes inflicted by the one-electron reduction of the N-heterocyclic molecule are observed in the vicinity of the N-centers bearing the highest effective nuclear charge. The DME-chelated metal cations coordinate at the N electron pairs and form Met⊕(DME)-bridged polymer chains of the radical anion, which are differently ondulated in the Na⊕ and K⊕ radical anion salts. The take-home lesson suggests that many more N-heterocyclic molecules might be analogously reduced under optimized conditions and isolated as single crystals. 相似文献
122.
Thorsten Oldag Thomas Aussieker Hans‐Lothar Keller Christian Preitschaft Arno Pfitzner 《无机化学与普通化学杂志》2005,631(4):677-682
Solvothermal Synthesis and Crystal Structure Determination of AgBiI4 and Ag3BiI6 AgBiI4 and Ag3BiI6 were synthesized by solvothermal reaction from AgI and BiI3 in diluted HI‐solution (20 %) at a temperature of 160 °C. The greyish‐black crystals grow as octahedra (AgBiI4) or hexagonal/trigonal platelets (Ag3BiI6). AgBiI4 crystallizes in space group Fd3¯m with a = 1222.3(1) pm (300 K) and Z = 8 whereas Ag3BiI6 shows the space group R3¯m with a = 435.37(6) pm, c = 2081.0(4) pm (300 K) and Z = 1. Both crystal structures show stacking sequence abcabc… of hexagonal layers containing Iodine. Bismuth and silver are sharing octahedral sites with different mass ratio in both structures. The part of silver which could be localized varies with temperature. This behaviour indicates mobility of silver within the crystal structure. The ionic conductivity of AgBiI4 is explored. AgBiI4 and Ag3BiI6 show close structural relationship, with AgBiI4 as a variant with a higher degree of order. 相似文献
123.
From 4-N-protected-aminopyridines which were functionalized at their 3-position, 5-azaisatin and equivalent synthons where obtained. Via the use of the Pfitzinger reaction, these compounds provided an easy route to new and various polyheterocyclic compounds. 相似文献
124.
Ivette Garcia CastroAnnegret Tillack Christian G HartungMatthias Beller 《Tetrahedron letters》2003,44(15):3217-3221
The one-pot synthesis of several branched secondary aliphatic amines is described. Hydroamination of terminal alkynes with aliphatic primary amines in the presence of Cp2Ti(η2-Me3SiCCSiMe3) gives the corresponding aldimines as intermediates. Reaction of these in situ produced aldimines with organolithium reagents (n-BuLi, PhLi) provides the α-branched amines in an easy way in upto 78% overall yield. 相似文献
125.
Hale KJ Frigerio M Manaviazar S Hummersone MG Fillingham IJ Barsukov IG Damblon CF Gescher A Roberts GC 《Organic letters》2003,5(4):499-502
[structure: see text] The synthesis of two truncated bryostatin analogues 2 and 3 is described. High-field NMR measurements on the C-ring analogue 3 in C(2)H(3)CN containing 25% (2)H(2)O have shown that it binds to the CRD2 of human PKC-alpha at virtually the same position as phorbol-13-acetate (PA) and bryostatin 1 (1). NMR titration studies have also revealed that 3 binds to the CRD2 with a potency similar in magnitude to PA but much less potently than 1. 相似文献
126.
Bringmann G Pfeifer RM Rummey C Hartner K Breuning M 《The Journal of organic chemistry》2003,68(18):6859-6863
The enantioselective synthesis of a novel-type C(3)-symmetric tripodal ligand that is composed of a central mesitylene-derived core and three functionalized, axially chiral biaryl subunits is described. The triol (M,M,M)-3 is a suitable catalyst for the enantioselective addition of dialkylzinc to various aromatic aldehydes with asymmetric inductions of up to 98% ee. 相似文献
127.
Bernard Chantegrel Christian Deshayes Bernard Pujol Zhong Jia Wei 《Journal of heterocyclic chemistry》1990,27(4):927-934
The title compounds were prepared from ethyl 5-acyl- or 5-(1-hydroxyethenyl)isoxazole-4-carboxylates which in turn were prepared from ethyl 3-methylamino-2-butenoate or 3(2H)-furanones. 相似文献
128.
Philippe Remuzon Daniel Bouzard Claire Clemencin Christian Dussy Munir Essiz Jean-Pierre Jacquet Jean Saint-Germain 《Journal of heterocyclic chemistry》1993,30(2):517-523
The synthesis of (1S,4S,7S)- and (1R,4R,7S)-2-(4-tolylsulfonyl>5-phenylmethyl-7-rnethyl-2,5-diazabicyclo-[2.2.1]heptanes ( 20 ) and ( 22 ) from trans 4-hydroxy-L-proline is described. 相似文献
129.
Mafra L Paz FA Shi FN Rocha J Trindade T Fernandez C Makal A Wozniak K Klinowski J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):363-375
A compound formulated as (C4H12N2)[Ge2(pmida)2(OH)2] x 4 H2O (where pmida(4-) = N-(phosphonomethyl)iminodiacetate and C4H12N2(2+) = piperazinedium cation), containing the anionic [Ge2(pmida)2(OH)2]2- complex, has been synthesised by the hydrothermal approach and its structure determined by single-crystal X-ray diffraction analysis. Several high-resolution solid-state magic-angle spinning (MAS) NMR techniques, in particular two-dimensional 1H-X(13C,31P) heteronuclear correlation (HETCOR) and 1H-1H homonuclear correlation (HOMCOR) experiments incorporating a frequency-switched Lee-Goldburg (FS-LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic-organic hybrids. We assigned the NMR resonances with the help of C...H and P...H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X-ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry). 相似文献
130.
Maurice Prost Marcel Urbain Andr Schumer Christian Houben Clment Van Meerbeeck 《Helvetica chimica acta》1975,58(1):40-49
The authors describe the synthesis of decahydro-4-quinolinones and N-substituted 4-alkynyl-, 4-allyl- and 4-alkyldecahydro-4-quinolinols and discuss the stereochemical problems of this compounds. 相似文献