- Anion- and Solvent-Induced Single-Crystal-to-Single-Crystal Transformation within an Iron(II) Triazole System: A Promising Luminescent Probe for CrO42- and Cyano-Containing Molecules
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Anion- and solvent-induced single-crystal-to-single-crystal transformation within an iron(II) triazole system has been generated from {[Fe(TPPT)2Cl2]·CHCl3}n (1a) to [Fe(TPPT)(C2O4)0.5Cl(H2O)]n (1b). Luminescence studies indicated that the resultant 1b can be considered as a promising luminescent probe for CrO42- and cyano molecules.
- Wang, Ying,Chen, Ran,Jia, Wei,Wang, Qian,Xue, Chong-Yu,Fan, Jia-Hui,Qi, Wan-Ru,Qin, Yue-Juan,Pan, Yu-Hua,Yang, Rong-Rong
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Read Online
- Oxa[7]superhelicene: A π-Extended Helical Chromophore Based on Hexa-peri-hexabenzocoronenes
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A novel π-extended “superhelicene” based on hexa-peri-hexabenzocoronenes (HBCs) has been synthesized by an efficient four-step synthetic procedure starting from diphenyl ether. Comprehensive structural analysis of the helicene was performed by NMR spectroscopy and mass spectrometry measurements together with X-ray analysis. Physicochemical analysis of the superhelicene and suitable HBC references revealed it had outstanding fluorescent features with quantum yields of over 80 %.
- Reger, David,Haines, Philipp,Heinemann, Frank W.,Guldi, Dirk M.,Jux, Norbert
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- Brominated Diphenyl Ethers - an Important Step on the Way to Synthetic Lubricants
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The described synthesis of synthetic lubricants based on polyphenyl ethers requires an analytical characterization of the isomerization step, which is important to the process optimization.The separation of the intermediates succeeds with gas chromatography; the isomers are determined using a retention index system.The obtained results are compared with the composition of the final product, which was investigated by HPLC analysis.Keywords.Gas chromatography; Polyphenyl ethers; Lubricants, synthetic.
- Kreisel, Guenter,Rudolph, Gundula,Schulze, Dieter Karl-Wilhelm,Poppitz, Wolfgang
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- Cadmium(II)–Triazole Framework as a Luminescent Probe for Ca2+and Cyano Complexes
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A bidentate ligand, 1-{4-[4-(1H-1,2,4-triazol-1-yl)phenoxy]phenyl}-1H-1,2,4-triazole (TPPT), has been designed and synthesized. By using TPPT as a building block for self-assembly with Cd(NO3)2?4 H2O and CdCl2?10.5 H2O, novel 1D double-chain {[Cd(TPPT)(NO3)2]?3 H2O}n(1) and 2D (4,4) layer [Cd(TPPT)Cl2(H2O)]n(2) have been constructed. When 1 was employed as a precursor and exposed to DMF or N,N′-dimethylacetamide (DMAC), the crystals of 1 dissolved and reassembled into two types of brown block-shaped crystals of 1D double chains: {[Cd(TPPT)2(NO3)2]?DMF}n(1 a) and {[Cd(TPPT)2(NO3)2]?DMAC}n(1 b). The anion-exchange reactions of complex 2 have also been investigated. After gently stirring crystals of 2 in CHCl3/C2H5OH/H2O containing NaBr, NaI?2 H2O, or NaOAc?3 H2O, the crystals retained their crystalline appearances. A remarkable single crystal to single crystal transformation was observed and 1D double chains of {[Cd(TPPT)Br2]?C2H5OH}n(2 a) and {[Cd(TPPT)2I2]?CHCl3}n(2 b), and 1D single chains of [Cd(TPPT)(H2O)2(CH3COO)2]n(2 c), can be obtained. Luminescent properties indicate that 1 shows excellent selectivity for Ca2+and cyano complexes. To the best of our knowledge, this is the first example of a luminescent probe for Ca2+based on triazole derivatives.
- Wang, Ying,Xu, Ping,Xie, Qiong,Ma, Qing-Qing,Meng, Yan-Hui,Wang, Zi-Wen,Zhang, Shaowei,Zhao, Xiao-Jun,Chen, Jun,Wang, Zhong-Liang
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Read Online
- Preparation method of 4-phenoxy phenylboronic acid
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The invention discloses a preparation method of 4-phenoxy phenylboronic acid, which belongs to the technical field of organic boric acid chemistry. The preparation method comprises the following steps: starting from diphenyl ether, reacting with NBS to generate 4,4'-dibromo diphenyl ether, reacting with borate and butyl lithium by a one-pot method, and hydrolyzing to obtain 4-phenoxy phenylboronicacid. According to the method, dibromides which are easy to purify are generated during bromination, monosubstituted products are generated by controlling the using amount of a lithiation reagent andthe boric acid ester during lithiation, the method is verified on the scale of 100 kg, and the method has the prospect of industrial methods.
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Page/Page column 4-6
(2020/05/14)
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- Industrial preparation method of 4, 4 '-dibromo diphenyl ether and 4, 4'-dihydroxy diphenyl ether
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The invention relates to an industrial preparation method of 4, 4 '-dibromo diphenyl ether and 4, 4'-dihydroxy diphenyl ether, and belongs to the technical field of organic synthesis. The method comprises the following steps: heating diphenyl ether and a catalyst in a reaction kettle to 20-100 DEG C, stirring, dropwise adding bromine, and controlling the temperature to be gradually increased alongwith the adding amount of the bromine so as to obtain a 4, 4 '-dibromo diphenyl ether crude product; absorbing hydrogen bromide gas generated in the reaction process by III grade water to prepare hydrobromic acid, wherein the reaction is carried out under a micro-negative pressure condition; recrystallizing the obtained 4, 4 '-dibromo diphenyl ether crude product by adopting an organic solvent toobtain the 4, 4'-dibromo diphenyl ether; and further adding sodium hydroxide, a catalyst and deionized water, carrying out a hydrolysis reaction, and carrying out post-treatment to prepare the 4, 4 '-dihydroxy diphenyl ether. Energy and raw material consumption can be effectively reduced, and the effects of high product efficiency, good quality and low cost are achieved. Effective environmental protection measures are taken in the production process, and a tail gas absorption device and sewage treatment facilities are arranged to effectively control and treat three wastes, so that the three wastes meet the emission standard.
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Paragraph 0042-0047
(2020/08/29)
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- Synthesis method of brominated hydroxydiphenyl ether compound (by machine translation)
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The brominated diphenyl ether compound is prepared by brominating diphenyl ether into a three- port bottle provided with a thermometer and a; reflux condenser pipe, wherein a proper amount of the activated carbon catalyst 60mL is, added with a, 1.0 g proper amount of, the activated carbon catalyst and then 30% the H mass fraction is added at a time. 2 O2, The product obtained by filtering and, separating the catalyst from the reaction solution after the constant,temperature reaction is several hours is completed, and the obtained product is, m-hydroxy-p,dibromodiphenyl, ether and. O-hydroxy-p-dibromodiphenyl ether, and the synthesis method is simple in process, low in cost and high in efficiency. (by machine translation)
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Paragraph 0006; 0018
(2019/12/31)
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- Regioselective Halogenation of Arenes and Heterocycles in Hexafluoroisopropanol
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Regioselective halogenation of arenes and heterocycles with N-halosuccinimides in fluorinated alcohols is disclosed. Under mild condition reactions, a wide diversity of halogenated arenes are obtained in good yields with high regioselectivity. Additionally, the versatility of the method is demonstrated by the development of one-pot sequential halogenation and halogenation-Suzuki cross-coupling reactions.
- Tang, Ren-Jin,Milcent, Thierry,Crousse, Benoit
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p. 930 - 938
(2018/01/28)
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- Solid-phase synthetic method and application of polybrominated diphenyl ether monomer
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The invention discloses a solid-phase synthetic method and application of a polybrominated diphenyl ether monomer. According to the solid-phase synthetic method and the application, the problems of an existing polybrominated diphenyl ether synthetic method that the reaction time is long, the reagent corrosivity is large, the postprocessing is complicated, and special equipment is required in the prior arts are solved. The solid-phase synthetic method has the beneficial effects that by utilizing a method of synthesizing polybrominated diphenyl ether through catalysis of solid superacid under a grinding condition, strong-base and strong-acid liquid reagents are not used, the safety is high, and the cleanness and the environmental protection are achieved; the synthesis time is 10-30 minutes, and compared with an ''iodonium salt-coupling two-step reaction method'', the reaction time is greatly shortened. According to the technical scheme, the solid-phase synthetic method comprises the step of enabling bromophenol to generate dehydration coupling reaction under the catalysis of solid superacid, so as to obtain the polybrominated diphenyl ether monomer.
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Paragraph 0048-0050
(2017/08/31)
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- Understanding the guanidine-like cationic moiety for optimal binding into the DNA minor groove
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Based on our previous positive results with bis-guanidine-like diaromatic compounds as DNA minor groove binders, we propose a new family: bis-2-amino-1,4,5,6-tetrahydropyrimidines. According to calculated parameters, these dicationic systems would have a more suitable size and lipophilicity for binding into the minor groove than previous series. Moreover, their DFT-optimised structures and docking into an AT oligomer model show that they would bind in the minor groove with good strength and without energy penalty. Hence, we prepared compounds 4 a-c and evaluated their binding to ssDNA and poly(dA-dT)2 by thermal denaturation experiments. The results showed that 4 a (CO) and 4 d (NH) were the best DNA binders. Compared to the previous series, 4 a-d are better binders than bis-guanidiniums but poorer than bis-2-aminoimidazolinium derivatives. Moreover, circular dichroism experiments using ssDNA and poly(dA-dT)2 confirmed binding into the minor groove. Based on our computational design as well as biophysical studies, we have been able to determine that the optimal interaction of guanidine-like dications in the minor grove occurs with bis-2-aminoimidazolinium systems.
- O'Sullivan, Patrick,Rozas, Isabel
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supporting information
p. 2065 - 2073
(2014/11/07)
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- Fe3O4@mesoporouspolyaniline: A highly efficient and magnetically separable catalyst for cross-coupling of aryl chlorides and phenols
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A high surface, magnetic Fe3O4@mesoporouspolyaniline core-shell nanocomposite was synthesized from magnetic iron oxide (Fe 3O4) nanoparticles and mesoporouspolyaniline (mPANI). The novel porous magnetic Fe3O4 was obtained by solvothermal method under sealed pressure reactor at high temperature to achieve high surface area. The mesoporouspolyaniline shell was synthesized by in situ surface polymerization onto porous magnetic Fe3O4 in the presence of polyvinylpyrrolidone (PVP) and sodium dodecylbenzenesulfonate (SDBS), as a linker and structure-directing agent, through 'blackberry nanostructures' assembly. The material composition, stoichiometric ratio and reaction conditions play vital roles in the synthesis of these nanostructures as confirmed by variety of characterization techniques. The role of the mesoporouspolyaniline shell is to stabilize the porous magnetic Fe3O4 nanoparticles, and provide direct access to the core Fe3O4 nanoparticles. The catalytic activity of magnetic Fe3O 4@mesoporousPANI nanocomposite was evaluated in the cross-coupling of aryl chlorides and phenols. Copyright
- Arundhathi,Damodara,Likhar, Pravin R.,Kantam, M. Lakshmi,Saravanan,Magdaleno, Travis,Kwon, Sun Hee
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supporting information; experimental part
p. 1591 - 1600
(2011/08/03)
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- Selective one-pot access to symmetrical or unsymmetrical diaryl ethers by copper-catalyzed double arylation of a simple oxygen source
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Great CO-mbination: A novel method is reported for the controlled one-pot synthesis of various symmetrical or unsymmetrical diaryl ethers by double arylation of a simple inorganic oxygen source (see scheme). This versatile and highly selective process is based on the use of a cheap and low toxicity copper catalytic system.
- Tlili, Anis,Monnier, Florian,Taillefer, Marc
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supporting information; experimental part
p. 12299 - 12302
(2011/02/16)
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- Efficient catalytic activity of copper/aluminum hydrotalcite in diaryl ether synthesis
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A simple copper/aluminum hydrotalcite (Cu/Al-HT) catalyzed arylation of phenols with aryl iodides afforded the corresponding diaryl ethers in moderate to excellent yields. This ligand- free Cu/Al-HT catalyzed coupling of aryl iodides with phenols resulted in high yields of diaryl ethers in the absence of an additive. The catalyst was quantitatively recovered from the reaction by simple filtration and reused for a number of cycles. Georg Thieme Verlag Stuttgart New York.
- Sreedhar,Arundhathi,Reddy, M. Amarnath,Kantam, M. Lakshmi
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experimental part
p. 483 - 487
(2009/07/11)
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- Regioselective bromination of activated aromatic substrates with a ZrBr4/diazene mixture
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A regioselective method for the bromination of phenols, ethers and anilines using a ZrBr4/diazene mixture is described. The reaction takes place under mild reaction conditions and the bromine atom adds first at the para unsubstituted position with respect to the OH, OR or NR2 group of the activated aromatic substrate. Less reactive compounds such as toluene, phenyl acetate, benzonitrile and trifluoromethylbenzene remain intact under the same conditions.
- Stropnik, Tadej,Bombek, Sergeja,Ko?evar, Marijan,Polanc, Slovenko
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p. 1729 - 1733
(2008/09/18)
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- Sodium nitrite-catalyzed oxybromination of aromatic compounds and aryl ketones with a combination of hydrobromic acid and molecular oxygen under mild conditions
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A novel and efficient catalytic system for the oxybromination of aromatic compounds and aryl ketones utilizing a combination of aqueous hydrobromic acid and molecular oxygen in the presence of sodium nitrite under mild conditions has been developed. The newly developed catalytic system utilizes cheap and readily available reactants, exhibits high bromine atom economy and releases only innocuous water as the by-product.
- Zhang, Guofu,Liu, Renhua,Xu, Qing,Ma, Lixin,Liang, Xinmiao
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p. 862 - 866
(2007/10/03)
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- Direct and regioselective iodination and bromination of benzene, naphthalene and other activated aromatic compounds using iodine and bromine
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Direct and regioselective iodination and bromination of benzene, naphthalene and other activated aromatic compounds with iodine and bromine or their sodium salts proceed well in the presence of Fe(NO3) 3·1.5N2O4/charcoal in CH 2Cl2 at room temperature.
- Firouzabadi,Iranpoor,Shiri
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p. 8781 - 8785
(2007/10/03)
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- Synthesis of polybrominated diphenyl ethers and their capacity to induce CYP1A by the Ah receptor mediated pathway
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Polybrominated diphenyl ethers (PBDEs) have become widely distributed as environmental contaminants due to their use as flame retardants. Their structural similarity to other halogenated aromatic pollutants has led to speculation that they might share toxicological properties such as hepatic enzyme induction. In this work we synthesized a number of PBDE congeners, studied their affinity for rat hepatic Ah receptor through competitive binding assays, and determined their ability to induce hepatic cytochrome P-450 enzymes by means of EROD (ethoxyre-sorufin-O-deethylase) assays in human, rat, chick, and rainbow trout cells. Both pure PBDE congeners and commercial PBDE mixtures had Ah receptor binding affinities 10-2-10-5 times that of 2,3,7,8-tetrachlorodibenzo-p-dioxin. In contrast with polychlorinated biphenyls, Ah receptor binding affinities of PBDEs could not be related to the planarity of the molecule, possibly because the large size of the bromine atoms expands the Ah receptor's binding site. EROD activities of the PBDE congeners followed a similar rank order in all cells. Some congeners, notably PBDE 85, did not follow the usual trend in which strength of Ah receptor binding affinity paralleled P-450 induction potency. Use of the gel retardation assay with a synthetic oligonucleotide indicated that in these cases the liganded Ah receptor failed to bind to the DNA recognition sequence.
- Chen,Konstantinov,Chittim,Joyce,Bols,Bunce
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p. 3749 - 3756
(2007/10/03)
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- Synthesis and characterization of 32 polybrominated diphenyl ethers
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Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame retardants in, for example, textiles, computers, television sets, and other electrical appliances. present also in humans. The environmental levels of the PBDEs are, however, still in general lower than those of polychlorinated biphenyls (PCBs). However, while the levels of PCBs generally are decreasing, those of the PBDEs are increasing in, for example, human milk. In the present study 32 individual PBDE congeners were synthesized and characterized. Physicochemical parameters including melting points and UV, 1H NMR, and mass spectra are reported Twenty-nine monobrominated to heptabrominated diphenyl ethers were synthesized by the couping between four diphenyliodonium salts and nine phenolates. One tetrabromodiphenyl ether and two hexabromodiphenyl ethers were synthesized by bromination of two different PBDEs. Twenty-one of the PBDEs and two of the iodonium salts, 2,2′,4,4′-tetrabromodiphenyliodonium chloride and 3,3′,4,4′-tatrabromodiphenyliodonium chloride, are to the authors' knowledge described for the first time. These synthesized reference compounds will aid in the identification and quantification of PBDEs present in environmental samples and will allow further assessment of PBDE toxicity.
- Marsh, Goeran,Hu, Jiwei,Jakobsson, Eva,Rahm, Sara,Bergman, Aeke
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p. 3033 - 3037
(2007/10/03)
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- Chalcogeno-Substituted Bis-triphenylmethylium Ions of the Inverse Malachite Green Type
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The longest wavelength VIS absorptions of the deeply colored CF3CO2H solutions of the 4,4'-chalcogenobis-(triphenylmethylium) ions 4(++), Y2 (Y = O, S, Se, Te) resemble closely those of the corresponding monocationic 4-arylchalcogenotriphenylmethylium systems 5(1+), ArYC6H4C(1+)(C6H5)2, and not those of the structurally directly related 4,4'-bis(arylchalcogeno)triphenylmethylium ions 3(1+), C6H5C(1+)(C6H4YAr)2.This is in striking contrast to the results obtained previously for analogous nitrogen systems, where "inverse", 2(++), RN, and "conventional" malachite green systems 1(+), (Ar2NC6H4)2C(1+)R, yield almost identical λmax values.A rationalization of these observations can be achieved based on the assumption of largely delocalized dications 2(++) versus more or less orthogonal "double monocationic" systems 4B(++), separated due to torsional twist.Whereas the formal push-pull systems 6(+), ArSC6H4YC6H4C(1+)(C6H5)2 (Y = O, S, Se) behaved practically like the corresponding standard systems 5(+), the mono- and bis-triphenylmethylthio-substituted dibenzofuran, dibenzothiophene and thioxanthene derivatives 8(+), 9(++), 10(+) and 11(++) displayed hypsochromic shifts of their color bands relative to their noncyclic analogues which are only partly in accordance with predictions based on a simple frontier orbital Hueckel model.The 1H and 13C NMR spectra of all these cationic species comply with their respective charges. +"--"+ Dyes, Chalcogeno-bis-trityliumions, VIS Spectra, NMR Spectra
- Hellwinkel, Dieter,Stahl, Heinz
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p. 521 - 538
(2007/10/02)
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- Process for the preparation of 4,4'-dibromodiphenylether
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4,4'-Dibromodiphenylether is prepared by reacting diphenylether with bromine and/or hydrobromic acid in the presence of one or more oxidizing agent(s), the reaction being carried out in a solvent comprising water and a water-immiscible organic solvent.
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- Regioselective Para Halogenation of Substituted Benzenes with Benzeneseleninyl Chloride and Aluminum Halide
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In the presence of aluminum halide, benzeneseleninyl chloride is an efficient regioselective halogenating reagent for activated aromatics such as toluene, phenol, anisole, phenetole, diphenyl ether, and N,N-dimethylaniline.Benzene and chlorobenzene are not halogenated under similar conditions.
- Kamigata, Nobumasa,Satoh, Takeshi,Yoshida, Masato,Matsuyama, Haruo,Kameyama, Masayuki
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p. 2226 - 2228
(2007/10/02)
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- Copper-catalyzed synthesis of phenol and diaryl ether derivatives: Via hydroxylation of diaryliodoniums
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A copper-catalysed hydroxylation of diaryliodoniums to generate phenols and diaryl ethers is reported. This method allows the synthesis of diversely functionalized phenols under mild reaction conditions without the need for a strong inorganic base or an expensive noble-metal catalyst. Significantly, convenient application of diaryliodoniums is demonstrated in the preparation of diaryl ethers in a one-pot operation.
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