Synthesis,Thermal Stability and Impact Stability of Novel Tetranitro‐Dipyridotetraazapentalene Derivatives

The synthetic details for the construction of three new dipyridotetraazapentalene derivatives, 5H‐pyrido[3″,4″:4′,5′] [1,2,3]triazolo‐ [1′,2′:1,2][1,2,3]triazolo[5,4‐b]pyridin‐6‐ium inner salt ( 8 ), 5H‐pyrido[3″,2″:4′,5′] [1,2,3]triazolo[1′,2′:1,2] [1,2,3]triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 15 ) and 5H‐pyrido[2″,3″:4′,5′] [1,2,3]‐triazolo[1′,2′:1,2][1,2,3]triazolo[4,5‐b]pyridin‐6‐ium inner salt ( 16 ) are presented. Nitration of ( 8 ) and ( 15 ) afforded the novel tetranitrodipyridotetraazapentalene derivatives, 2,4,8,10‐tetranitro‐5H‐pyrido[3″,4″:4′,5′][1,2,3]triazolo[1′,2′:1,2][1,2,3]‐triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 3 ) and 2,4,8,10‐tetranitro‐5H‐pyrido[3″,2″:4′,5′][1,2,3]triazolo[1′,2′:1,2][1,2,3]‐triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 4 ) in good yields. Both isomers, ( 3 ) and ( 4 ), exhibited high thermal stability (differential scanning calorimetric analysis and thermal gravimetric analysis) and were insensitive to impact (hammer/anvil test).     

Synthesis and adsorption properties,toward some heavy metal ions,of a new polystyrene‐based terpyridine polymer

A novel polymeric ligand having 2,2′:6′,2″‐terpyridine as pendant group was prepared through a Williamson type etherification approach for the reaction between 4′‐hydroxy‐2,2′: 6′,2″‐terpyridine and the commercially available 4‐chloromethyl polystyrene. The chelating properties of the new polymer toward the divalent metal ions (Cu²⁺, Zn²⁺, Ni²⁺, and Pb²⁺) in aqueous solutions was studied by a batch equilibration technique as a function of contact time, pH, mass of resin, and concentration of metal ions. The amount of metal‐ion uptake of the polymer was determined by using atomic absorption spectrometry. Results of the study revealed that the resin exhibited higher capacities and a more pronounced adsorption toward Pb²⁺ and that the metal‐ion uptake follows the order: Pb²⁺ > Cu²⁺ > Zn²⁺ > Ni²⁺. The adsorption and binding capacity of the resin toward the various metal ions investigated are discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Ligand Structure and Complexation,XLVIII Alkali and Alkaline Earth Metal Ion Complexes of Bipyridine,Phenanthroline and Terpyridine

Crystalline alkali and alkaline earth metal ion complexes of 2,2′-bipyridine and 2,2′:6′,2″-terpyridine are obtained and compared with known and new alkali and alkaline earth metal salt complexes of 1, 10-phenanthroline.     

系列三联吡啶衍生物的合成及在催化氧化中的应用

采用一步法合成了5种三联吡啶的衍生物:4′-(吡啶-4-基)-2,2′∶6′,2″-三联吡啶(L1)、4′-苯基-2,2′∶6′,2″-三联吡啶(L2)、4′-(3,5-二氯吡啶-4-基)-2,2′∶6′,2″-三联吡啶(L3)、4′-(3,5-二溴吡啶-4-基)-2,2′∶6′,2″-三联吡啶(L4)、4′-(4-(吡啶-4-基)苯基)-2,2′∶6′,2″-三联吡啶(L5),其中L3和L4为尚未见报道的新颖化合物。以制备的多吡啶化合物为配体,和MnCl₂·4H₂O共同催化苄基醇的氧化反应,研究发现5种多吡啶配体均具备良好的性能,配体分子结构中的4′-吡啶取代基对提高催化活性有重要作用。最后选用性能最优的4′-(4-(吡啶-4-基)苯基)-2,2′∶6′,2″-三联吡啶为配体,与MnCl₂·4H₂O共同催化叔丁基过氧化氢氧化苄基醇和苄基烷烃,5种典型底物的转化率均在95%以上,产率在90%以上。该催化氧化方法有望应用于芳香酮类化合物及相关药物中间体的绿色、高效合成。     

A double-stranded 1D-coordination polymer assembled using the tetravergent ligand 1,1′-bis(4,2′:6′,4″-terpyridin-4′-yl)ferrocene

1,1′-Bis(4,2′:6′,4″-terpyridin-4′-yl)ferrocene (1) reacts with ZnCl₂ to yield a double-stranded 1D-coordination polymer [{Zn₂(1)Cl₄}∙3CHCl₃]_n. The 1,1′-functionalized ferrocene core adopts a cisoid-conformation, giving rise to a folded conformation for 1 and a double-stranded 1D-polymer chain. This contrasts with previously reported multi-stranded chains supported by 4,2′:6′,4″-terpyridine ligands in which the multiple-nature of the chain arises from multinuclear metal nodes.     

Low-Temperature Crystallization for Separating Monoacetylated Long-Chain Sophorolipids: Characterization of Their Surface-Active and Antimicrobial Properties

Pseudohyphozyma (formerly Rhodotorula) bogoriensis synthesizes long-chain-length (22-carbon chain) sophorolipids (22:0-SL) that are variously acetylated at the 6′- or/and 6″-carbons of the sophorose unit. In this paper, we describe a low-temperature crystallization protocol that preferentially separates the 6′-monoacetylated 22:0-SL (6′-Ac₁-22:0-SL) from a parental mixture of 22:0-SL containing a majority (64.7%) of the 6′,6″-diacetylated moiety (6′,6″-Ac₂-22:0-SL), as deduced from high-pressure-liquid-chromatography evaporative-light-scattering-detection (HPLC-ELSD) and LC/Q-TOF-MS analyses. Tensiometry measurements using the Wilhelmy plate method yielded minimum-surface-tension (SFT_min) and critical-micelle-concentration (CMC) values of 34.6 ± 1.0 mN m⁻¹ and 0.014 mM, respectively, for 6′-Ac₁-22:0-SL (CRYSTAL) fraction and 34.9 ± 1.0 mM m⁻¹ (SFT_min) and 0.018 (CMC) for the hexane precipitate (Hx-PRCP) fraction containing a high concentration (89.2%) of the diacetylated 6′,6″-Ac₂-22:0-SL after crystal removal. In contrast, the SFT_min and CMC of the well-studied 16-18 carbon (C_16-18)-SL of Starmerella bombicola were 35–37.2 mN m⁻¹ and 0.05-(>0.3) mM, respectively. Individually, the purified CRYSTAL and Hx-PRCP fractions exhibited a similar degree of strong growth-inhibition activity against Cutibacterium (formerly Propionibacterium) acnes as determined by an agar-plate zone of inhibition assay. Study on the growth inhibition of oral health-related bacteria, i.e., Streptococcus mutans and Lactobacillus acidophilus, showed that, depending on the bacteria and strains tested, the CRYSTAL fraction was either slightly better than or equally effective as the Hx-PRCP fraction in inhibiting cell growth.     

Synthesis and characterization of novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives

Two novel phenyl‐substituted poly(p‐phenylene vinylene) derivatives, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylenevinylene} (EDP‐PPV) and poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDMP‐PPV), and their copolymer, poly{2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐1,4‐phenylene‐vinylene‐co‐2‐[3′,4′‐(2″‐ethylhexyloxy)(3″,7″‐dimethyloctyloxy)benzene]‐5‐methoxy‐1,4‐phenylenevinylene} (EDP‐co‐EDMP‐PPV; 4:1, 1:1, and 1:4), were successfully synthesized according to the Gilch route. The structures and properties of the monomers and the resulting conjugated polymers were characterized with ¹H‐NMR, ¹³C‐NMR, elemental analysis, gel permeation chromatography, thermogravimetric analysis, ultraviolet–visible absorption spectroscopy, and photoluminescence and electroluminescence (EL) spectroscopy. The EL polymers possessed excellent solubility in common solvents and good thermal stability with a 5% weight loss temperature of more than 380°C. The weight‐average molecular weights and polydispersity indices of EDP‐PPV, EDMP‐PPV, and EDP‐co‐EDMP‐PPV were 1.40–2.58 × 10⁵, and 1.19–1.52, respectively. Double‐layer light‐emitting diodes with the configuration of indium tin oxide/polymer/tris(8‐hydroxyquinoline)aluminum/Al devices were fabricated, and EDP‐co‐EDMP‐PPV (1:1) showed the highest EL performance and exhibited a maximum luminance of 1050 cd/m² at 19.5 V. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1259–1266, 2005     

Synthesis and characterization of polyphenylene vinylenes having <Emphasis Type="Italic">m</Emphasis>-terphenyl group: comparison of their optical properties

A series of alternate block copolymers of polyphenylene vinylenes that have 1,3-dioctyloxy phenylene in the center of kinked m-terphenyl group as one of the building blocks with either one of the aromatic groups, viz., 1,4-dioctyloxy benzene, 4,6-dioctyloxy benzene and 4,4′-dioctyloxy biphenyl, was synthesized through Heck polymerization. These alternate block copolymers, viz., poly(2,5-bis(octyloxy)phenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P1), poly(2,4-bis(octyloxy)phenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P2) and poly(4,4′-bis(octyloxy-3,3′-biphenylene vinylene alt 4′,6′-bis(octyloxy)-1,1′:3′,1″-terphenylene) (P3), were characterized for their thermal and optical properties. The synthesized polymers had good solubility in organic solvents and were stable up to 350 °C. The molecular weights of the synthesized polymers were in the range 4370–10,900 Da with polydispersity range 1.52–1.65, which were measured by the gel permeation chromatography technique. The optical properties of these polymers showed absorptions in solution at around 400, 329, and 345 nm for P1, P2, and P3 polymers, respectively. The photoluminescence emission maxima of the polymers were at around 461 nm with a shoulder 439 and 424 nm for P1, P2, and P3, respectively. Photoluminescence emission of films of these polymers showed minimum redshift (20 nm) when compared with spectra of their solutions. The optical and photoluminescence emission properties of these polymers were found to vary on the backbone structure.     

Crystallography and Structure–Property Relationships of 2,2″,4,4′,4″,6,6′,6″‐Octanitro‐1,1′ : 3′,1″‐Terphenyl (ONT)

An X‐ray crystallographic study of 2,2″,4,4′,4″,6,6′,6″‐octanitro‐1,1′ : 3′,1″‐terphenyl (ONT) has been carried out. The dihedral angles between benzene rings vary from 84.9° to 89.4°. Nonbinding interatomic distances of oxygen atoms inside all the nitro groups are shorter than the intermolecular contact radii for oxygen. On the basis of the DFT B3LYP/6‐31(d, p) method it was found that the difference between the X‐ray structure in the solid phase and DFT result for the gas phase is 98 kJ mol⁻¹, and the bearer of the highest initiation reactivity of the ONT molecule in the solid phase should be the nitro group at 4″‐position, in contrast to those at 4′‐ or 6′‐position that play this role in the isolated molecule. It has been stated that the nitro groups at the reaction centers of the ONT molecule are relatively well specified by their ¹⁵N NMR chemical shifts.     

New Bitopic Ligands for the Group Actinide Separation by Solvent Extraction

Abstract

The synthesis and evaluation of solvent extraction performance of N,N,N′,N′-tetraalkyl-6,6″-(2,2′:6′,2″-terpyridine)diamides and N,N′-diethyl-N,N′-diphenyl-6,6″-(2,2′:6′,2″-terpyridine)diamide are reported here. These new bitopic ligands were found to extract actinides in different oxidation states (U(VI), Np(V and VI), Pu(IV), Am(III), and Cm(III)) from 3 M nitric acid. The presence of three soft nitrogen donors led to the selective extraction of actinides(III) over lanthanides(III) (Ce, Eu) and the presence of two amide functional groups grafted to the terpyridine unit allowed the extraction to occur from a highly acidic medium by minimizing the basicity of the ligand. Ligands bearing long alkyl chains (C4 and C8) or phenyl groups showed increased performances in a polar diluent like nitrobenzene.     

Highly trans‐1,4‐specific polymerization of 1,3‐butadiene catalyzed by [2,6‐bis{(4S)‐ (−)‐isopropyl‐2‐oxazolin‐2‐yl}pyridine] chromium complex activated with modified methylaluminoxane

Chromium complexes with N,N,N‐tridentate ligands, LCrCl₃ (L = 2,6‐bis{(4S)‐(?)‐isopropyl‐2‐oxazolin‐2‐yl}pyridine ( 1 ), 2,2′:6′,2″‐terpyridine ( 2 ), and 4,4′,4″‐tri‐tert‐butyl‐2,2′:6′,2″‐terpyridine ( 3 )), were prepared. The structures of 1 and 2 were determined by X‐ray crystallography. Upon activation with modified methylaluminoxane (MMAO), 1 catalyzed the polymerization of 1,3‐butadiene, while 2 and 3 was inactive. The obtained poly(1,3‐butadiene) obtained with 1 ‐MMAO was found to have completely trans‐1,4 structure. The 1 ‐MMAO system also showed catalytic activity for the polymerization of isoprene to give polyisoprene with trans‐1,4 (68%) and cis‐1,4 (32%) structure. Copyright © 2011 Society of Chemical Industry     

3,1′-Bridged 2-[2′-(4″-dialkylaminophenyl)ethenyl] pyrylium and 1-Benzopyrylium Dyes – Synthesis and Vis/NIR Absorption/Emission Behaviour

A series of new 3,1′-bridged 2-[2′-(4″-dialkylaminophenyl)ethenyl]-4,6-diarylpyrylium perchlorates ( 3 ), 2-[2′-(4″-dialkylaminophenyl)ethenyl]-7-diethylamino-1-benzopyrylium perchlorates 5–8 , 2-[4′-(4″-dialkylaminophenyl)butadien-1′,3″-yl]-, and 2-[2′-(7″-diethylaminocoumar-3″-yl)ethenyl]-7-diethylamino-1-benzopyrylium perchlorates 10–12 were synthesized and characterized by means of elemental analysis, m.p., Vis/NIR, and ¹H NMR spectra. Semiempirical MO calculations were performed to elucidate the essential features of the chromophores. The size of the bridging ring strongly affects the geometry of the chromophores which, in turn, determines the extent of charge transfer of the longest wavelength electronic transition. Increasing deviation from planarity causes the polymethine-like chromophore to become more polyene-like.     

Crystallography and Structure–Property Relationships in 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐Dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐ Quaterphenyl (DODECA)

X‐ray crystallographic study of 2,2′,2″,2′′′,4,4′,4″,4′′′,6,6′,6″,6′′′‐dodecanitro‐1,1′ : 3′1″ : 3″,1′′′‐quaterphenyl (DODECA) has been carried out. Nonbonding interatomic distances of oxygen atoms inside of all the nitro groups are shorter than those corresponding to the intermolecular contact radii for oxygen. By means of the DFT B3LYP/6‐31(d, p) method a difference of 136 kJ mol⁻¹ between the X‐ray and DFT structures of DODECA was found. The bearer of the highest initiation reactivity in its molecule in solid phase should be the nitro group at 4′′′‐position, in contrast to those at 2′‐ or 2″‐positions in its isolated molecule. The most reactive nitro group in the DODECA molecule can be well specified by the relationship between net charges on nitro groups and charges on their nitrogen atoms, both of them for the X‐ray structure. The ¹⁵N chemical shift, corresponding to this nitro group for the initiation by impact and shock, correlates very well with these shifts of the reaction centers of the other six “genuine” polynitro arenes.     

甲基取代三苯胺类化合物的合成

以氯化亚铜、1,10-邻菲咯啉为催化剂,二苯胺及其衍生物与对碘甲苯经U llm ann反应合成了4-甲基三苯胺(MTPA)、4,4′-二甲基三苯胺(DMTPA)和4,4,′4″-三甲基三苯胺(TMTPA),收率分别达到了94.61%、94.76%和94.93%,产物的HPLC纯度都高于99.50%,并用红外光谱、元素分析及质谱对产物结构和组成进行了鉴定。     

One-Pot Formation of a Metallosupramolecularly Assembled and Redox-Active Adlayer at the Solid–Liquid Interface

A redox-active adlayer consisting of cobalt ions and terpyridine ligands, 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine), was prepared on a Au(111) surface by a stepwise coordination method. The obtained adlayer produced a well-defined, stable redox wave associated with cobalt ions coordinated to 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine), as compared to a tetra-2-pyridinyl-pyrazine adlayer, for which no redox wave was observed. In situ scanning tunneling microscopy revealed a structural change in the redox-active adlayer consisting of 4′,4′′′′-(1,4-phenylene)bis(2,2′:6′,2′′-terpyridine) and cobalt ions. It was found that the ability of cobalt ions to coordinate on Au(111) was clearly dependent on the chemical structure of the ligand, suggesting that ligand coordination with metal ions on the Au surface is determined by the molecular orientation and configuration of the ligand when the ligand is adsorbed on a Au substrate.     

Nitro explosive and cation sensing by a luminescent 2D Cu(I) coordination polymer with multiple Lewis basic sites

A new 2D Cu(I)-based coordination polymer with Lewis basic sites based on pytpy (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine) ligand, [Cu(pytpy)(CN)]_n(1), has been synthesized solvothermally and characterized. The photoluminescence property shows that 1 can work as highly sensitive sensors to nitro explosive and Fe^3 + by luminescent quenching. This study demonstrated that 1 could be a useful luminescent sensor for metal ions and organic small molecules.     

Synthesis and Self-assembling Properties of 2,2′:6′,2″-Terpyridine-Based Carbon Nanotube Coordination Polymers

A novel metallo-supramolecular polytopic ligand was synthesized from the attachment reaction involving an amino group-functionalized multi-wall carbon nanotube and 4-chloro-2,2′:6′,2″-terpyridine used for the preparation of metallo-supramolecular polymers with Co(II) or Ni(II) ions. Different colors were observed depending on either the ligands or the metal ions in this type of supramolecular assembly. The created supramolecular polymers were characterized by means of structure, morphology, and stimuli-responsive performance employing scanning electron microscopy, amperometric techniques, UV–Vis and Fourier transform infrared spectroscopy. UV–Vis spectroscopy and cyclic voltammetry studies confirmed that both the optical and electrochemical properties of metallo-supramolecular materials are affected by the substituent at the pyridine periphery.     

泰利霉素重要中间体3-氧代-6-O-甲基红霉素的合成

由克拉霉素的前体6-O-甲基-2′,4″-二(三甲基硅)-红霉素A9-(1-异丙氧基环己基)肟(Ⅰ)出发,常温下以φ(HC l)=10%的盐酸催化水解得3-羟基-6-O-甲基红霉素A9肟(Ⅱ);然后一锅煮进行化合物Ⅱ的2′-羟基乙酰化、3-羟基氧化,得2′-乙酰基-3-氧代-6-O-甲基红霉素A9-(O-乙酰基)肟(Ⅳ);最后脱乙酰基、还原9-肟基再次应用一锅煮法合成,得到目的化合物3-氧代-6-O-甲基红霉素(Ⅵ),总收率为57.0%,经HPLC测定w(Ⅵ)=98.5%。通过1HNMR1、3CNMR和MS,表征了各中间体及目标化合物的结构。     

Synthesis and characterization of poly(1-sila-cis-pent-3-enes) substituted with pendant pyridinyl groups

Poly[1-methyl-1-[3′-(3″-pyridinyl)propyl]-1-sila-cis-pent-3-ene], poly[1-phenyl-1-[3′-(3″-pyridinyl)propyl)-1-sila-cis-pent-3-ene], and poly[1-phenyl-1-(4′-pyridinyl)-1-sila-cis-pent-3-ene] were synthesized by the anionic ring-opening polymerization of 1-methyl-1-[3′-(3″-pyridinyl)propyl]-1-silacyclopent-3-ene, 1-phenyl-1-[3′-(3″-pyridinyl)propyl]-1-silacyclopent-3-ene, and 1-phenyl-1-(4′-pyridinyl)-1-silacyclopent-3-ene, respectively. These are the first polycarbosilanes which contain heterocyclic pyridine units as side-chain substituents. These polymers were characterized by¹H,¹³C, and²⁹Si NMR as well as by IR and UV spectroscopy. The molecular weight distributions were determined by gel permeation chromatography, glass transition temperatures, by differential seanning calorimetry: (DSC) and thermal behavior, by thermogravimetric analysis. (TGA).