Novel Host Compounds, 1,1′-Binaphthyl-2,2′-Dihydroxy-5,5′- and 6,6′-Dicarboxylic Acid, which Trap Guest Molecules Tightly in their Inclusion Crystals

The host compounds 1,1’-binaphthyl-2,2′-dihydroxy-5,5′-dicarboxylic acid (1) and 1,1′-binaphthyl-2,2′-dihydroxy-6,6′-dicarboxylic acid (2) have been synthesized, and their inclusion properties have been studied. Inclusion complexes formed by 1 and 2 with volatile guests such as acetone and methanol release the guests only at much higher temperatures than their boiling points. The crystal structures of the inclusion complexes have been determined from single crystal X-ray diffraction data and show different host lattices.     

Phosphorylation of Tetrahydric Phenols with Trivalent Phosphorus Compounds. Synthesis of Tetraphosphites

The reactions of 1,1'-spirobi(5,6-dihydroxy-3,3-dimethylindane) and 1,2,4,5-tetrahydroxybenzene with 2-chloro-1,2,3-dioxaphosphorinanes of various structure were used to obtain tetraphosphorylated systems. Investigation of the chemical properties of the products was initiated. Basing on 1,1'-spirobi(3,3-dimethylindane-5,6-diyl) tetra(2,2-dimethylpropanediyl phosphite), a Pt(II) chelate was synthesized.     

一种手性性质随不同金属离子改变的共轭聚合物

化学传感器能识别一种特殊分子或一类分子的分子装置 ,基于共轭聚合物的化学传感器的设计原理一般都是利用其分子的电子效应和空间构象的变化 [1～ 4] ,而旋光分子的手性同样与其电子和空间结构相关 .本文试图建立一种依靠化合物手性 (如旋光度 )的变化检测金属离子的新方法 .由于含手性联萘结构的共轭聚合物具有较好的旋光热稳定性和高的旋光值 [5,6] ,以及聚合物主链上联吡啶基团可与许多过渡金属离子配位[4,7] ,我们设计合成了一种同时含有联吡啶和手性联萘基团的共轭聚合物 .结果表明 ,不同过渡金属离子与聚合物联吡啶单元的作用可引起…     

Affinity of a new copper(II) complex to DNA/BSA and antioxidant/radical scavenging activities: crystal structure of [Cu(4,7-diphenyl-1,10-phenanthroline)(leucine)(NO3)(H2O)]

A new copper(II) complex, [Cu(Bphen)(Leu)(NO₃)(H₂O)] (Bphen = 4,7-diphenyl-1,10-phenanthroline, leu = L-leucine), has been synthesized and characterized by IR spectroscopy, CHN analysis, and single-crystal X-ray diffraction techniques. The CT-DNA binding properties of the complex have been investigated by both absorption and emission spectroscopy. The binding parameters for the fluorescence Scatchard plot were also determined. Further, the interaction of the complex with bovine serum albumin (BSA) has been investigated using absorption and emission spectroscopy. The thermodynamic parameters, free energy change (ΔG), enthalpy change (ΔH), and entropy change (ΔS), were calculated by the van’t Hoff equation and discussed. The distance between BSA and the complex has been obtained according to fluorescence resonance energy transfer. Conformational changes of BSA have been observed from synchronous fluorescence. Antioxidant and radical scavenging activities of the complex were determined by various in vitro assays such as 1,1-diphenyl-2-picryl-hydrazyl free radicals (DPPH˙), 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radicals (ABTS˙⁺), and reducing ability determination by H₂O₂ scavenging methods.     

Phosphomacrocyclic systems based on 2,2′-dihydroxy-1,1′-dinaphtylmethane

For the first time phosphomacrocyclic systems were synthesized based on 2,2′-dihydroxy-1,1′-dinaphthylmethane, other aromatic diols, and phosphorous hexaethyltriamide. Spontaneous transformation of the obtained macrocycles into the more stable 1,3,2-dioxaphosphacyn and cyclobisamidophosphite was established.     

Facile synthesis of 6-iodo-2,2′-dipivaloyloxy-1,1′-binaphthyl, a key intermediate of high reactivity for selective palladium-catalyzed monofunctionalization of the 1,1′-binaphthalene core

A high-yielding procedure for selective monoiodination of 2,2′-dihydroxy-1,1′-binaphthyl (BINOL) is reported. 6-Iodo-2,2′-dipivaloyloxy-1,1′-binaphthyl, obtained in three steps starting from BINOL in 88% overall yield, proved to be a highly efficient substrate in various palladium-catalyzed coupling (Stille, Heck, Sonogashira, and Suzuki coupling) and carbonylation reactions compared to the analogous 6-bromo derivative.     

1,1-二氨基-2,2-二硝基乙烯的合成研究进展

1,1-二氨基-2,2-二硝基乙烯（FOX-7）是一种低感度高能量的新型含能材料.现有的1,1-二氨基-2,2-二硝基乙烯的合成包括以2-甲基咪唑、盐酸乙脒与乙二酸二乙酯、2-甲基-4,6-二羟基嘧啶为前体的三条合成路线.使用硫酸/硝酸体系硝化2-甲基-4,6-二羟基嘧啶可得到2-二硝基亚甲基-5,5-二硝基嘧啶-4,6-二酮,然后水解可得到FOX-7,正相硅胶薄层色谱可对该反应进行监测.使用曲拉通X-100/正己烷体系的反相微乳法可制备FOX-7球形纳米晶;FOX-7球形纳米晶具有良好的应用前景,对其合成工艺与路线进行探索和研究具有一定的意义.     

Some Specific Features of Acid Nitration of 2-Substituted 4,6-Dihydroxypyrimidines. Nucleophilic Cleavage of the Nitration Products

The nitration of 2-substituted 4,6-dihydroxypyrimidines in concentrated sulfuric acid yields the corresponding 5,5-dinitro derivatives. When the substituent in position 2 is an alkyl group, the nitration occurs both at position 5 and at the -carbon atom of the side chain. Hydrolysis of 2-substituted 4,6-dihydroxy-5,5-dinitropyrimidines leads to formation of 1,1-diamino-2-R-2-nitroethylene derivatives. 1,1-Diamino-2,2-dinitro-ethylene was obtained by nitration of 4,6-dihydroxy-2-methylpyrimidine and subsequent hydrolysis of 4,6-dihydroxy-5,5-dinitro-2-(dinitromethylene)-2,5-dihydropyrimidine.     

Thermal decomposition of several N,N′-bis(2-hydroxyiminoalkyl)-α,α′-dinitrones

Journal of Thermal Analysis and Calorimetry - N,N′-Bis(2-hydroxyiminoalkyl)-α,α′-dinitrones are of interest for the synthesis of 1,1′-dihydroxy-2,2′-biimidazoles....     

Highly enantioselective reduction of alkynyl ketones by a binaphthol-modified aluminum hydride reagent. Asymmetric synthesis of some insect pheromones

Alkynyl ketones can be reduced to chiral propargylic alcohols by a complex aluminum hydride modified by chiral 2,2′-dihydroxy-1,1′-binaphthyl. The synthetic utility has been demonstrated by the synthesis of the Japanese beetle and rove beetle pheromones.     

2,2′‐Diamino‐6,6′‐diboryl‐1,1′‐binaphthyl: A Versatile Building Block for Temperature‐Dependent Dual Fluorescence and Switchable Circularly Polarized Luminescence

Temperature‐dependent dual fluorescence and switchable circularly polarized luminescence (CPL) are two highly pursued but challenging properties for small organic molecules (SOMs). We herein disclose a triarylborane π‐system based on a 2,2′‐diamino‐6,6′‐diboryl‐1,1′‐binaphthyl scaffold that can serve as a versatile building block for achieving these two properties by simply choosing different amino groups. BNMe₂‐BNaph with less bulky dimethylamino groups displays temperature‐dependent dual fluorescence, and can thus be used as a highly sensitive ratiometric fluorescence thermometer. On the other hand, BNPh₂‐BNaph with bulky diphenylamino groups exhibits intense fluorescence in both solution and in the solid state. A change of solvent from nonpolar cyclohexane to highly polar MeCN not only shifts the CPL position to much longer wavelength but also inverts the CPL sign. In addition, the complexation of BNPh₂‐BNaph with fluoride greatly enhances the CPL intensity.     

Preparation and properties of aromatic polyamides from 2,2′-bis(p-carboxyphenoxy) biphenyl or 2,2′-bis(p-carboxyphenoxy)-1,1′-binaphthyl and aromatic diamines

New aromatic dicarboxylic acids having kink and crank structures, 2,2′-bis(p-carboxyphenoxy) biphenyl and 2,2′-bis(p-carboxyphenoxy)-1,1′-binaphthyl, were synthesized by the reaction of p-fluorobenzonitrile with biphenyl-2,2′-diol and 2,2′-dihydroxy-1,1′-binaphthyl, respectively, followed by hydrolysis. Biphenyl-2,2′-diyl-and 1,1′-binaphthyl-2,2′-diyl-containing aromatic polyamides having inherent viscosities of 0.58–1.46 dL/g and 0.63–1.30 dL/g, respectively, were obtained by the low-temperature solution polycondensation of the corresponding diacid chlorides with aromatic diamines. These polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, m-cresol, and pyridine. Transparent, pale yellow, and flexible films of these polymers could be cast from the DMAc or NMP solutions. These aromatic polyamides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 210–272 and 260–315°C, respectively. They began to lose weight around 380°C, with 10% weight loss being recorded at about 450°C in air. © 1993 John Wiley & Sons, Inc.     

Stereoselective synthesis of chiral atropisomerically stable ferrocenyldiols containing a biphenyl unit

Two different ferrocenyldiketones 1 and 2 containing a biphenyl unit were prepared by Ni(0) promoted homocoupling of suitable ferrocenyl-aryl halides. The atropisomeric stability of the corresponding diols and other related derivatives was investigated. Chiral 2,2′-bis-(ferrocenylhydroxymethyl)-1,1′-biphenyl, (−)-5c, and 1(1,1′)-ferrocena-2,5-dihydroxy-3,4(1,2)dibenzenacyclopentaphane, (+)-6a and (−)-6b, were prepared as single diastereoisomers with defined central and axial chiralities by CBS-catalyzed asymmetric reduction of 1 and 2, respectively. During the reaction, that proceeded with high stereoselectivity affording the above mentioned diols in satisfactory enantiomeric excess, we noticed the occurrence of an unusual reductive deoxygenation process. Absolute configurations of the chiral diols were assigned by means of X-ray crystallographic and circular dichroism analyses.     

Preparation and properties of aromatic polyamides from 2,2′-bis(p-aminophenoxy) biphenyl or 2,2′-bis(p-aminophenoxy)-1,1′-binaphthyl and aromatic dicarboxylic acids

New aromatic diamines having kink and crank structures, 2,2′-bis(p-aminophenoxy)biphenyl and 2,2′-bis(p-aminophenoxy)-1,1′-binaphthyl, were synthesized by the reaction of p-fluoronitrobenzene with biphenyl-2,2′-diol and 2,2′-dihydroxy-1,1′-binaphthyl, respectively, followed by catalytic reduction. Biphenyl-2,2′-diyl- and 1,1′-binaphthyl-2,2′-diyl-containing aromatic polyamides having inherent viscosities of 0.44–1.18 and 0.26–0.88 dL/g, respectively, were obtained either by the direct polycondensation or low-temperature solution polycondensation of the diamines with aromatic dicarboxylic acids (or diacid chlorides). These polymers were readily soluble in a variety of organic solvents including N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, m-cresol, and pyridine. Transparent, pale yellow, and flexible films of these polymers could be cast from the DMAc or NMP solutions. These aromatic polyamides containing biphenyl and binaphthyl units had glass transition temperatures in the range of 215–255 and 266–303°C, respectively. They began to lose weight at ca. 380°C, with 10% weight loss being recorded at about 470°C in air. © 1993 John Wiley & Sons, Inc.     

Multistimuli-responsive benzothiadiazole-cored phenylene vinylene derivative with nanoassembly properties

A trifluoromethyl-substituted benzothiadiazole-cored phenylene vinylene fluorophore (1) was synthesized and displayed piezo- and vapochromism and thermo-induced fluorescence variation in solid phase. Grinding could disrupt the crystalline compound 1 with orange emission into amorphous compound 1 with green emission, and heating treatment could change the amorphous compound 1 into crystalline compound 1. Ultraviolet-visible (UV-vis) absorption spectra, (13)C nuclear magnetic resonance (NMR), and powder X-ray diffraction (PXRD) characterizations demonstrated that crystalline and amorphous compound 1 possess different molecular packing. A differential scanning calorimetry (DSC) measurement revealed that the emission switching was due to the exchange between the thermodynamic-stable crystalline and metastable amorphous states. The ground sample exhibited vapochromic fluorescence property. Furthermore, compound 1 showed interesting supramolecular assembly characteristics in solution. Slowly cooling the hot N,N-dimethylformamide (DMF) solution of compound 1 resulted in the formation of orange fluorescent fibers, whereas sonication treatment of the cooling solution led to the generation of organic molecular gel. The field emission scanning electronic microscope (FESEM) and fluorescent microscopy images revealed smooth nano- or microfiber and network morphology properties. The PXRD spectra confirmed that these nano- or microstructures had a similar molecular-packing model with the crystalline state of compound 1. Slow evaporation of the toluene solution of compound 1 could produce green emissive microrods, which exhibited interesting thermo-induced fluorescence variation.     

Synthesis and chiroptical properties of chiral binaphthyl‐containing polyfluorene derivatives

New chiral binaphthyl‐containing polyfluorene (PF) derivatives, PFOH , PFMOM , and PFP , bearing different binaphthyl units ((S)‐2,2′‐bis(methoxymethoxy)‐1,1′‐binaphthyl for PFMOM , (S)‐1,1′‐binaphthyl‐2,2′‐diol for PFOH , and (S)‐2,2′‐bis(diphenylphosphinyl)‐1,1′‐binaphthyl for PFP ) in the backbone have been designed and synthesized through Pd‐catalyzed Suzuki polycondensation. Their properties have been investigated in detail by ¹H NMR, ¹³C NMR, TGA, DSC, UV–vis, photoluminescence (in solutions, in thin films before and after annealing), and circular dichroism (CD) spectroscopic methods compared with poly(9,9‐dihexylfluorene‐2,7‐diyl) ( PF ). The resulting copolymers possessed excellent solubility in organic solvents and emitted strong blue light. The phosphine oxide‐containing copolymers PFP and PFMOM exhibited higher quantum yields and better thermal spectral stability in comparison with PF . All the copolymers exhibited obviously the linearly polarized photoluminescent properties both in solutions and in solid states. High emission polarization ratios (R_PL) of PFP were observed with no obvious decrease upon thermal annealing. In addition, investigation of the CD spectroscopic properties of these copolymers in THF solutions indicated that the chirality of the binaphthyls could be transferred to the whole PF backbone. All these results demonstrated that introduction of the chiral binaphthyls, particularly BINAPO, into the backbone could effectively improve the performances of the copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Effect of ring torsion on intramolecular vibrational redistribution dynamics of 1,1'-binaphthyl and 2,2'-binaphthyl

The role of ring torsion in the enhancement of intramolecular vibrational energy redistribution (IVR) in aromatic molecules was investigated by conducting excitation and dispersed fluorescence spectroscopy of 1,1'-binaphthyl (1,1'-BN) and 2,2'-BN. The dispersed fluorescence spectra of 1,1'-BN in the origin region of S(1)-S(0) were well resolved, which presented 25-27 cm(-1) gaps of torsional mode in the ground state. The overall profile of the dispersed spectra of 1,1'-BN is similar to that of naphthalene. In contrast, the spectra of 2,2'-BN were not resolved due to the multitude of the active torsional modes. In both cases, dissipative IVR was observed to take place with a relatively small excess vibrational energy: 237.5 cm(-1) for 1,1'-BN and 658 cm(-1) for 2,2'-BN, which clearly shows that ring torsion efficiently enhances the IVR rate. Ab initio and density functional theory calculations with medium-sized basis sets showed that the torsional potential of 1,1'-BN has a very flat minimum over the range of torsional angles from ca. 60° to 120°, whereas that of 2,2'-BN showed two well-defined potential minima at ca. 40° and 140°, in resemblance to the case of biphenyl. In this work, we propose that aromatic molecules be classified into "strong" and "weak" torsional hindrance cases: molecules with strong hindrance case show shorter torsional progressions and more effective IVR dynamics than do those with weak hindrance.     

Chiral recognition of binaphthyl derivatives using electrokinetic chromatography and steady-state fluorescence anisotropy: effect of temperature

The effect of temperature on the chiral recognition of binaphthyl derivatives in the presence of poly sodium N-undecanoyl-LL-leucyl-leucinate (poly LL-SULL) is examined using electrokinetic chromatography (EKC) and steady-state fluorescence anisotropy. An examination of the effect of temperature suggests that the chiral recognition of 1,1'-binaphthyl-2,2'-diol enantiomers improves with increasing temperature, whereas lower temperatures resulted in better enantiosolectivity in the case of 1,1'-binaphthyl-2,2'-diyl hydrogen phosphate enantiomers. In addition, steady-state fluorescence anisotropy results show that the anisotropy of the two enantiomers are different when complexed to poly-(LL) SULL. As would be expected, the enantiomer that binds stronger to the chiral pseudostationary phase, as evidenced by EKC experiments, had higher anisotropy values. The results of this study suggest that steady-state fluorescence anisotropy can be used to gain further insight into chiral recognition.     

Syntheses of dibenzo[c,e][1,2]diselenin and related novel chalcogenide heterocyclic compounds

Reaction of 2,2′-dilithio-1,1′-binaphthyl with selenium followed by air oxidation gives a mixture of dinaph-thoselenophene and dimer and oligomers of 2,2′-diseleno-1,1′-binaphthyl. 2,2′-Dilithio-1,1′-biphenyl reacts with selenium to afford dibenzo[c,e][1,2]diselenin. Structures of the dimeric 2,2′-diseleno-1,1′-binaphthyl and dibenzo[c,e][1,2]diselenin have been confirmed by X-ray crystallographic analyses. Similar reaction of 2,2′-dilithio-1,1′-binaphthyl with sulfur or tellurium gives a mixture of dinaphthothiophene and dinaphtho[2,1-c:-1′,2′-e][1,2]dithiin or a mixture of dinaphthotellurophene and oligomer of 2,2′-ditelluro-1,1′-binaphthyl, respectively. Dibenzotellurophene and oligomer of 2,2′-ditelluro-1,1′-biphenyl are obtained from reaction of 2,2′-dilithio-1,1′-biphenyl with tellurium.     

Novel silica-based hybrid materials incorporating binaphthyl units: a chiral matrix effect in heterogeneous asymmetric catalysis

Polysilsesquioxane hybrid materials containing chiral binaphthyl moieties are readily available by coupling (R)- or (S)-2,2′-dihydroxy-1,1′-binaphthyl (BINOL) with 3-(triethoxysilyl)propyl isocyanate and subsequent hydrolysis polycondensation of the resulting bis-trialkoxysilylated carbamate precursor. Rhodium species were embedded in the chiral hybrid matrix. The catalytic properties of the solids were evaluated in hydride-transfer reduction to prochiral ketones. When the catalytic species were embedded in an entirely chiral network, enantiomeric excesses up to 45% were observed.