4'-(丹磺酰氨基)苯并冠醚和4'-[α-(丹磺酰氨基)乙基]苯并-15-冠-5的合成

从B12C4, B15C5和B18C6经过硝化、催化氢化和丹磺酰化合成了三种4'-(丹磺酰氨基)苯并冠醚, 从B15C5径乙酰化, Leuckart反应和丹磺酰化合成了另一个4'-[α-(丹磺酰氨)乙基]苯并-15-冠-5这些丹磺酰氨衍生物均为新荧光冠醚.     

Separation of (3R, 3′ R)-, (3R, 3′ S; meso)-, (3S, 3′ S)- Zeaxanthin, (3R, 3′ R, 6′ R)-, (3R, 3′ S, 6′ S)- and (3S, 3′ S, 6′ S)-Lutein via the dicarbamates of (S)-(+)-α-(1-naphthyl) ethyl isocyanate

A method is described for the qualitative and quantitative determination of configurational isomers of zeaxanthin (=3,3′ -dihydroxy-β, β -carotene) and lutein (=3,3′ -dihydroxy-α -cartotene). It is based on the reaction of these zeaxathin and lutein isomers with (S)-(+)-α-(1-naphthyl) ethyl isocyanate to afford diastereomeric dicarbamates, which are analyzed by HPLC.     

Phthalocyanine polymers. I. Poly[2,2′-(4,4′,4″-,4‴-metal phthalocyanino)-5,5′-bibenzimidazoles] as new high temperature resistant polymers

A novel class of poly(metal phthalocyanino) benzimidazoles were prepared by the condensation reaction between metal (Cu, Co, and Zn), 4,4′,4″,4?-tetracarboxyphthalocyanine, and 3,3′-diaminobenzidine. The reaction was investigated by melt and solution condensation methods. These polymers showed excellent thermal and thermooxidative stability and are noteworthy for their high char yield (86–90%) at 800°C in an anerobic atmosphere. Elemental analyses, spectra, and TGA studies were used to characterize these materials. Isothermal gravimetric analyses were carried out to determine their long-term thermal stability.     

Synthesis and Spectroscopic Properties of Cyclotriphosphazenes Containing 6-（4-Hydroxyphenyl）-2,2′-bipyridine Side Groups

Two novel cyclotriphosphazene derivatives containing 6- （4-hydroxyphenyl）-2,2′-bipyridine （hopbp） side groups, N3 P3 （dobp） 2 （hopbp） 2 （ 1 ） and N3 P3 （dobp） （hopbp） 4 （2） （ dobp = 2,2′-dioxybiphenyl）, were synthesized and characterized. These compounds display strong fluorescent emission both in solution and in solid state. Their absorption and emission spectra are sensitive to proton： the addition of HBF4 to the methanol and dichloromethane solution（9： 1, volume ratio） of compound 1 led to a red-shift from 350 to 460 nm for the emission spectrum, and the process was also characterized by isosbestic points of absorption spectra at 267, 287 and 313 nm.     

Saturated heterocycles. 242. Synthesis of 2-substituted-6-(6′,7′-dimethoxy-3′,4′-dihydro-1′-isoquinolyl)-5,6,7,8-tetrahydro- quinazolin-4(3H)-one Derivatives

In the reactions of the recently synthesized β-ketoesters 1-[(3′-methoxycarbonyl- and 1-[(3′-ethoxycarbonyl-4′-oxo)-1′-cyclohexyl]-3,4-dihydroisoquinoline 4, 5 with amidines or cyclic guanidines, a number of 2-substituted-6-(6′,7′-dimethoxy-3′,4′-dihydro-1′-isoquinolyl)-5,6,7,8-tetrahydroquinazolin-4(3H)-one derivatives 6–8 were prepared. The new compounds possess various pharmacological actions.     

Crystal Structures of Chiral Ionophores: Bis(9,9′-spirobifluorene)-26-crown-4 and -32-crown-6

The X-ray crystal structures of bis(9,9′-spirobifluorene)-26-crown-4βbenzene solvate (monoclinic, a = 15.47 Å, b 11.265 Å, c = 15.220 Å, β = 91.54°, space group C2) and bis(9,9′-spirobifluorene)-32-crown-6·dichloromethane solvate (tetragonal, a = 20.958 Å, c = 11.779 Å, space group P4₁2₁2) are described. Both compounds act as enantioselective ionophores for α-aminoalcohols.     

Synthesis of C-5 benzoyl and azido functionalized 2,2′-dithiobis-and 2,2′-diselenobis(1H-indoles)

Novel methods for the synthesis of C-5 benzoyl and azido analogues of 2,2′-dithiobis(1H-indole), 1, and 2,2′-diselenobis(1H-indole), 2, are described to further explore the structure activity relationships in this region of the molecule. Analogues 3-i displayed inhibitory activity (IC₅₀ = 0.45-2.03 μ) toward the catalytic domain of the epidermal growth factor receptor tyrosine kinase that was equivalent to or better than that of unsubstituted compounds 1 and 2. The regiochemistry of Friedel-Crafts benzoylation onto 1 was determined by X-ray crystallography. To test the potential for compounds of this class to interact with the epidermal growth factor receptor tyrosine kinase via a sulfhydryl exchange mechanism, reaction of a 2,2′-dithiobis(1H-indole) with glutathione was carried out and the product characterized.     

Synthesis and spectroscopic properties of 4-(4-carboxyphenyl)-3,3′,5′-trimethyl-2,2′-pyrromethen-1,1′-BF2 complex and its methyl ester

A new, strongly absorbing red dipyrrole chromophore 1 suitable for exciton coupling studies has been synthesized and shown to exhibit an intense absorption (?? 57,000) at λ (max) ?520 nm and a strong fluorescence at λ (em) ?555 nm.     

5-(α-Fluorovinyl)tryptamines and 5-(α-Fluorovinyl)-3-(N-methyl-1′,2′,5′,6′,-tetrahydropyridin-3′- and -4′-yl)indoles—5-(α-Fluorovinyl)tryptamines

5-(α-Fluorovinyl)tryptamines 4a, 4b and 5-(α-fluorovinyl)-3-(N-methyl-1′,2′,5′,6′-tetrahydropyridin-3′- and -4′-yl) indoles 5a, 5b were synthesized using 5-(α-fluorovinyl)indole ( 7 ). The target compounds are bioisosteres of 5-carboxyamido substituted tryptamines and their tetrahydropyridyl analogs.     

Crowned polyacetylene. I. Synthesis and characterization of poly(4′-ethynylbenzo-15-crown-5)

4′-Ethynylbenzo-15-crown-5 ( EB15C5 ) polymerized with high yields in the presence of (bicyclo[2.2.1] hepta-2,5-diene) rhodium(I) chloride dimer and triethylamine as a cocatalyst in chloroform at 30°C. Common catalysts for the polymerization of substituted acetylenes, WCl₆ and MoCl₅, did not produce any polymer from EB15C5 . The structure of the main chain for poly(4′-ethynylbenzo-15-crown-5) ( PEB15C5 ) was determined to be predomi-nantly cis form, based upon the relatively sharp signals attributed to the main chain atoms that was observed in the ¹H and ¹³C NMR spectra. The cation-binding properties of PEB15C5 are very similar to that of poly(4′-vinylbenzo-15-crown-5), and the selectivity is in the order of K⁺> Rb⁺ ? Cs⁺ ? Na⁺, Li⁺. The electrical conductivity of PEB15C5 increased from 1.3 × 10^?10 to 1.3 × 10^?6 S. cm^?1, when the polymer was doped with iodine. © 1995 John Wiley & Sons, Inc.     

Cobalt(II) and cobalt(III) complexes with 4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine

4′‐Cyanophenyl‐2,2′:6′,2′′‐terpyridine (cptpy) was employed as an N,N′,N′′‐tridentate ligand to synthesize the compounds bis[4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine]cobalt(II) bis(tetrafluoridoborate) nitromethane solvate, [Co^II(C₂₂H₁₄N₄)₂](BF₄)₂·CH₃NO₂, (I), and bis[4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine]cobalt(III) tris(tetrafluoridoborate) nitromethane sesquisolvate, [Co^III(C₂₂H₁₄N₄)₂](BF₄)₃·1.5CH₃NO₂, (II). In both complexes, the cobalt ions occupy a distorted octahedral geometry with two cptpy ligands in a meridional configuration. A greater distortion from octahedral geometry is observed in (I), which indicates a different steric consequence of the constrained ligand bite on the Co^II and Co^III ions. The crystal structure of (I) features an interlocked sheet motif, which differs from the one‐dimensional chain packing style present in (II). The lower dimensionality in (II) can be explained by the disturbance caused by the larger number of anions and solvent molecules involved in the crystal structure of (II). All atoms in (I) are on general positions, and the F atoms of one BF₄⁻ anion are disordered. In (II), one B atom is on an inversion center, necessitating disorder of the four attached F atoms, another B atom is on a twofold axis with ordered F atoms, and the C and N atoms of one nitromethane solvent molecule are on a twofold axis, causing disorder of the methyl H atoms. This relatively uncommon study of analogous Co^II and Co^III complexes provides a better understanding of the effects of different oxidation states on coordination geometry and crystal packing.     

Synthesis of 2-(o-chloropheny)- and 2-(2′,6′-dichlorophenyl)-4-formyl-1,2,3-triazoles

Mesoaldehyde 1,3-dioxime was treated with either o-chlorophenyl- or 2,6 dichloro-phenylhydrazine to give the corresponding 2-chlorophenylhydrazone. Hydrazones 1a and 1b were treated with acetic anhydride and cyclized to triazoles ( 3a and 6a ) with cesium carbonate. These were then hydrolized to the previously unknown chlorophenyltriazole aldehydes ( 4a and 4b ). They were also converted to a number of acid derivatives, alcohols, and amines.     

Preparation of 1,1′-binaphthyl-2,2′-diyl bridged ansa-bis( annulated cyclopentadienyl) titanium and -zirconium dichloride complexes

The coupling of enantiomerically enriched 2,2′-dilithio-1,1′-binaphthyl with various annulated cyclopentenones or 2-indanone proves to be a facile route for the preparation of a series of annulated bis(cyclopentadienes) or bis(indenes) bridged at a symmetrical cyclopentadienyl position. The six- or seven-membered annulated bis(tetrahydroindene) 6 or bis(hexahydroazulene) 7 ligands could readily be converted to titanium or zirconium dichloride complexes. Owing to the symmetry of the ligands, only a single C₂-symmetrical isomer of the metallocene dichloride could form. Although the faces of the cyclopentadienyl moieties are homotopic, the chiral bridge enforces a chiral conformation of the metallocene complexes. The bis(indenyl) 5 or five-membered annulated bis(tetrahydropentalene) 8 ligands could not be metalated. Unbridged 2-methyl and 2-phenyl substituted tetrahydropentalenes 27 and 28 were prepared and could readily be converted to titanium dichloride complexes.     

Mass spectra of some 2-(4′-butyl-3,′5′-dimethylpyrazol-1′-yl)-6-substituted benzothiazoles

The fragmentation of the title compounds on electron impact has been studied and the major processes interpreted. The base peak invariably appears at [M ? 43]⁺ whose origin from the butyl chain has been traced with the help of metastable ion studies and accurate mass measurements. Loss of methyl cyanide, involving the decomposition of the pyrazole moiety, is observed only from the fragment ions.     

Isothermal degradation of poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole

The isothermal degradation of poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole in vacuo has been studied. Measurement of the increase in pressure with time, coupled with infrared analysis, was used to determine the distribution of the degradation products. Processes A and B with different second-order rate laws were determined to be significant in the temperature range of 550–700°C. Process A leads to the formation of equimolar quantities of hydrogen and ammonia and has an activation energy of 68 kcal/mole. Process B leads to the production of HCN, NH₃, and H₂ in the ratio of 1:1:2.5 and has an activation energy of 77 kcal/mole. The activation energies and the rate laws are consistent with a mechanism in which the initial degradation step is the bimolecular reaction of two aromatic rings.