- Metal complexation of thioacylferrocenes: crystal structures of pentacarbonyl(thiobenzoylferrocene-S)chromium and benzoylferrocene
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Acylferrocenes (C5H5)Fe(C5H4COR) (R=CH3, C2H5, (CH3)2CH, (CH3)3C or Ph) can be readily thionated to give thioacylferrocenes by use of P4S10 in non-polar solvents such as CH2Cl2 or toluene; use of polar solvents such as THF or diglyme provides very poor conversions.Thiobenzoylferrocene reacts readily with Et4N+-- (M = Cr, Mo, or W) in the presence of silver nitrate to yield (C5H5)Fe>, in which the M(CO)5 group is bonded to the sulphur atom as revealed by an X-ray diffraction study.The structure consists of isolated molecules in which a Cr(CO)5 fragment of approximate C4v symmetry is bonded via sulphur to the thioacylferrocene with an Cr-S bond length of 2.412(1) Angstroem, an S=C bond length of 1.667(2) Angstroem and a C-S-Cr angle of 121.9(1) deg.Photo oxidation of (C5H5)Fe> yields benzoylferrocene the crystal structure of which was determined.
- Barnes, John C.,Bell, William,Glidewell, Christopher,Howie, R. Alan
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- Improvement of ferrocene acylation. Conventional vs. microwave heating for scandium-catalyzed reaction in alkylmethylimidazolium-based ionic liquids
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Acylation of ferrocene-catalyzed by scandium triflate was thoroughly investigated. Reaction time and temperature are important parameters, in that prolonged treatment causes substrate decomposition and/or catalyst deactivation. Hydrophobic alkylmethylimid
- Berardi, Serena,Conte, Valeria,Fiorani, Giulia,Floris, Barbara,Galloni, Pierluca
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- Generation of ferrocenylvinyl cation CpFeC5H4–C+=CH2 by protonation of ferrocenylacetylene with Nafion and its reactions with SMe2 and PPh3 in scCO2 giving onium salts
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Cation CpFeC5H4–C+=CH2 was obtained by protonation of FcC[tbnd6]CH with Nafion superacid in DMF or scCO2 and characterized by NMR spectroscopy. The protonation in the presence of SMe2 or PP
- Kizas, Ol'ga A.,Chaschin, Ivan S.,Godovikov, Ivan A.,Dolgushin, Fedor M.,Antonov, Dmitrii Yu.,Nikitin, Lev N.,Khokhlov, Alexei R.
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- The synthesis of ferrocenyl- and ferrocenoylpyrimidines
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New derivatives of pyrimidine were synthesized from ferrocenyl ketones by the reactions of [3+1+1+1]annulation and intermolecular cyclization. The electrochemical behavior of the obtained compounds was studied by the method of cyclic voltammetry. All the
- Zherebker,Rodionov,Pilipenko,Kachala,Nikitin,Belousova,Simenel
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- Palladium-Catalyzed Removable 8-Aminoquinoline Assisted Chemo- and Regioselective Oxidative sp2-C-H/sp3-C-H Cross-Coupling of Ferrocene with Toluene Derivatives
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The coupling of the C(sp2)-H bond of ferrocene with toluene avoiding in situ functionalization of both coupling partners has been achieved using palladium and iron dual catalysis. This cross oxidative coupling features regioselectivity to prima
- Sattar, Moh.,Kumar, Sangit
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- Fabrication of bisferrocenyl derivative grafted HTPB with high iron content and its application in dopamine detection
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In this work, we employed an efficient strategy to increase the graft percentage of ferrocene in hydroxyl terminated polybutadiene (HTPB) polymer framework. For this purpose, we use 5-chloro-2-pentanone to attach the two alkylferrocene derivatives to each other. In order to incorporate the obtained bis-alkylferrocene derivatives to the polymer backbone, the chlorine atom at the end of the coupling agent alkyl chain was converted to a silane group using the Grignard reaction. Finally, hydrosilylation reaction of as-synthesized silane derivatives and HTPB in the presence of Speier's catalyst (H2PtCl6) resulted in novel bis-ferrocene modified HTPBs with a variety of iron contents. The iron percentage, viscosity, and glass transition temperature of the novel bis-ferrocene modified HTPBs as essential parameters of polymer characterization were investigated. Obtained polymers are electro-active due to the presence of ferrocenyl groups. Additionally, unlike the virgin polymer (HTPB) they show optical properties. The final polymer was immobilized onto the bare glassy carbon electrode (GCE) surface using the cross-linking effect of terephthaldehyde (TFA) and fresh egg white (FEW). Electrochemical impedance spectroscopy (EIS) confirmed the successful immobilization of the polymer. The ability of the fabricated electrode to mediate dopamine (DA) oxidation was evaluated, and the results show the acceptable detection limits as well as linear ranges for the determination of dopamine using GC/BEFcHTPB/(TFA+FEW).
- Aghaiepour, Alireza,Rahimpour, Shabnam,Payami, Elmira,Mohammadi, Reza,Teimuri-Mofrad, Reza
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- Very high rate enhancement of benzyl alcohol oxidation by an artificial enzyme
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(Figure Presented) Promoting the atomic dialogue! At neutral pH and ambient temperature, a cyclodextrin-derived ketone causes hydrogen peroxide and benzyl alcohols to meet in its active site and react up to 60 000 times faster than they do outside the cyclodextrin.
- Marinescu, Lavinia G.,Bols, Mikael
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- Tuneable superbase-catalyzed vinylation of α-hydroxyalkylferrocenes with alkynes
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Superbase-catalyzed (KOH/DMSO suspension as a catalyst) vinylation of hydroxymethyl- and hydroxyethylferrocenes with terminal and internal alkynes (acetylene, propyne, phenylacetylene, 3-ethynylpyridine, 1-propyn-1-yl-benzene, diphenylacetylene) affords hitherto unknown vinyl ethers of ferrocene in 30-93% yields depending on the alkyne structure and the tuneable ratio of reactants/KOH/DMSO. The vinylation smoothly proceeds under mild conditions (70-90 °C, 0.25-13 h). With unsubstituted acetylene the process is readily realized under atmospheric pressure (yield of the corresponding vinyl ethers is 81-90%) though under pressure (initial pressure at room temperature is 10-13 atm, maximum pressure is 13-16 atm at the reaction temperature) the yield is close to quantitative (93%). The synthesized compounds were characterized using 1H and 13C NMR, and IR spectroscopy, as well as X-ray diffraction analysis.
- Trofimov, Boris A.,Oparina, Ludmila A.,Tarasova, Olga A.,Artem'ev, Alexander V.,Kobychev, Vladimir B.,Gatilov, Yuriy V.,Albanov, Alexander I.,Gusarova, Nina K.
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- Synthesis, characterization and electrochemical properties of novel trinuclear ferrocenyl based organosilane compounds
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Some trinuclear ferrocenyl based organosilane compounds were synthesized by hydrosilylation reaction of [4-(ethylferrocenyl)butyl]dimethylsilane and (4-ferrocenylbutyl)dimethylsilane with bisalkenylferrocene derivatives, in the presence of the Karstedt catalyst at room temperature. In addition a simple method for the preparation of 1,1′-bis(3-butenyl)alkylferrocenes from 1,1′-bis(4-chlorobutyl)alkylferrocenes under mild conditions was developed. 1H and 13C NMR, FT-IR, GC-MS, CHN analysis, atomic absorbtion spectroscopy supported the predicted structure of the products. The electrochemical behavior of synthesized compounds was studied by cyclic voltammetry in CH3CN/0.1 M LiClO4 utilizing a glasse carbon working electrode. The relationship between the peak currents and the square root of the scan rate, showed that the redox process is diffusion limited.
- Teimuri-Mofrad, Reza,Safa, Kazem D.,Rahimpour, Keshvar
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- Assembly of dendrimers with redox-active [{CpFe(μ3-CO)} 4] clusters at the periphery and their application to oxo-anion and adenosine-5′-triphosphate sensing
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9, 16, or 27 [CpFe(μ3-CO)]4 clusters contain the title assemblies (see picture). The one-electron oxidation Fe 4→Fe4+of all Fe4 units appears as a single reversible cyclic voltammetry wave and was used in solution and with dendrimer-modified electrodes for oxo-anion recognition. ATP2- is selectively recognized and better than H2PO4-. The larger the dendrimer, the easier is the re-use of the modified electrode sensor. (Chemical Equation Presented)
- Aranzaes, Jaime Ruiz,Belin, Colette,Astruc, Didier
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- Synthesis and liquid crystal properties of copper(II) and palladium(II) chelates with new ferrocene-containing enaminoketones
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Heterometallic liquid crystals are of special interest because of the possibility to combine optical, magnetic and electric properties of different metal ions in one mesogenic molecule. In order to investigate new heteropolynuclear mesogenic systems, a se
- Kadkin, Oleg N.,Kim, Eun Ho,Kim, So Yeon,Choi, Moon-Gun
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- Synthesis of new binuclear ferrocenyl compounds by hydrosilylation reactions
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Ferrocenyl silanes are prepared by treatment of Grignard reagents produced from 4-chlorobutylferrocene derivatives and chlorodimethylsilane in THF. Butenylferrocenes are prepared by the elimination reaction of 4-chlorobutylalkylferrocenes by sodium tert-butoxide in DMSO. A hydrosilylation reaction between a butenyl compound and ferrocenylsilane occurred in dry toluene at room temperature in the presence of the Karstedt catalyst to produce the desired binuclear ferrocenyl compound in good to high yields. The electrochemical behavior of new ferrocenyl compounds were studied by cyclic voltammetry in CH3CN/0.1?M LiClO4, and the relation between the peak currents and the square root of the scan rate, showed that the redox process is diffusion-limited.
- Teimuri-Mofrad, Reza,Mirzaei, Farzaneh,Abbasi, Hassan,D. Safa, Kazem
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- A step towards development of promising trypanocidal agents: Synthesis, characterization and in vitro biological evaluation of ferrocenyl Mannich base-type derivatives
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Chagas disease is a neglected chronical parasitosis caused by the parasite Trypanosoma cruzi (T. cruzi). Nine ferrocenyl Mannich base derivatives were synthetized and characterized to explore their in vitro activity on three T. cruzi strains of the parasite and their cytotoxicity on Vero cells to calculate the selectivity index (SI). Compound 2, 1-ferrocenyl-3-(4-(4-(trifluoromethyl)phenyl)piperazin-1-yl)propan-1-one, stood out as the most promising derivative showing a half maximal inhibitory concentration (IC50) value around 5 μM in both amastigote and trypomastigote forms of T. cruzi and SI values higher than 13, being the best value on the trypomastigote forms of the Arequipa strain (SI = 41.7). Moreover, 2 decreased the number of infected cells and was not genotoxic. Furthermore, its possible mechanism of action was studied through the alteration of the metabolites excreted by the parasite during glucose metabolism, the detection of mitochondrial alterations and the inhibition of superoxide dismutase (SOD). Finally, docking studies were executed to analyze the binding mode of the studied compounds to Fe-SOD enzyme.
- Paucar, Rocío,Martín-Escolano, Rubén,Moreno-Viguri, Elsa,Cirauqui, Nuria,Rodrigues, Carlos Rangel,Marín, Clotilde,Sánchez-Moreno, Manuel,Pérez-Silanes, Silvia,Ravera, Mauro,Gabano, Elisabetta
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- Copper and nickel complexes of the tetradentate ligand derived from the condensation of ferrocenoylacetone with 1,2-diaminoethane
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Ferrocenoylacetone [C5H5FeC5H 4C(O)CH2C(O)CH3] reacts with 1,2-diaminoethane in refluxing ethanol to yield three isolated isomers H2L, H 2L1 and H2L2. In solution, H 2L1 and H2L2 can change into H 2L on standing over two days. Reaction of the tetradentate enaminone ligand [C5H5FeC5H4C(O)CH=C(CH 3)NHCH2]2 (H2L) with hydrated copper acetate and nickel acetate affords complexes I (LCu) and II (LNi). All compounds have been characterized by elemental analyses, 1HNMR, IR and UV spectroscopies. The X-ray crystallography of complexes I and II reveals that the enaminone dianion coordinates to the central metal ion (copper and nickel) via two oxygen and two nitrogen atoms, and complex I exists as a mixture of the anti and syn isomers in a molar ratio of 1:1 while the complex II exists as a single syn isomer.
- Shi, Yao-Cheng,Shen, Wen-Bin,Yang, Hua-Mei,Song, Hai-Bin,Hu, Xiao-Ya
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- The d4/d3 redox pairs [MX(CO)(η-RCCR)Tp′] z (z = 0 and 1): Structural consequences of electron transfer and implications for the inverse halide order
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The d4 halide complexes [MX(CO)(η-RCCR)Tp′] {X = F, Cl, Br or I; R = Me or Ph; M = Mo or W; Tp′ = hydrotris(3,5- dimethylpyrazolyl)borate} undergo one-electron oxidation to the d3 monocations [MX(CO)(η-RCCR)Tp′]+, isolable for M = W, R = Me. X-Ray structural studies on the redox pairs [WX(CO)(η-MeCCMe)Tp′] z (X = Cl and Br, z = 0 and 1), the ESR spectra of the cations [WX(CO)(η-RCCR)Tp′]+ (X = F, Cl, Br or I; R = Me or Ph), and DFT calculations on [WX(CO)(η-MeCCMe)Tp′]z (X = F, Cl, Br and I; z = 0 and 1) are consistent with electron removal from a HOMO (of the d4 complexes) which is π-antibonding with respect to the W-X bond, π-bonding with respect to the W-C(O) bond, and δ-bonding with respect to the W-Calkyne bonds. The dependence of both oxidation potential and ν(CO) for [MX(CO)(η-RCCR)Tp′] shows an inverse halide order which is consistent with an ionic component to the M-X bond; the small size of fluorine and its closeness to the metal centre leads to the highest energy HOMO and the lowest oxidation potential. In the cations [MX(CO)(η-RCCR)Tp′] + electronegativity effects become more important, leading to a conventional order for Cl, Br and I. However, high M-F π-donation is still facilitated by the short M-F distance. The Royal Society of Chemistry.
- Adams, Christopher J.,Bartlett, Ian M.,Carlton, Susannah,Connelly, Neil G.,Harding, David J.,Hayward, Owen D.,Orpen, A. Guy,Patron, Elena,Ray, Christopher D.,Rieger, Philip H.
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- Synthesis of 5-(dimethylsilyl)pentylalkylferrocene-grafted HTPB (alkylFc-HTPB) via platinum-catalyzed hydrosilylation
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In this work, at first alkylferrocene derivatives were synthesized according to procedure described in the literature. (5-Chloropentanoyl)ferrocene derivatives were prepared by Friedel–Crafts acylation of ferrocene and alkylferrocene derivatives with 5-ch
- Teimuri-mofrad, Reza,Safa, Kazem D.,Abedinpour, Saiedeh,Rahimpour, Keshvar
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- 1-Ethyl-3-methylimidazolium halogenoaluminate melts as reaction media for the Friedel-Crafts acylation of ferrocene
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Ionic liquid mediated Friedel-Crafts acylation of the organometallic complex ferrocene can be performed in 1-ethyl-3-methylimidazolium halogenoaluminate melts, EtMeimI-AlCl3, as well as in the liquid clathrate formed upon addition of an excess
- Surette, Jacqueline K. D.,Green, Laine,Singer, Robert D.
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- Synthesis and thermal performance of poly(cyclotriphosphazene- acetylferrocene) derivative
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Amino nucleophilic reagents were prepared by using acetylferrocene and diamines and then the iron-phosphazene derivative was first synthesized by the nucleophilic substitution reaction of hexachlorocyclotriphosphazene and the amino nucleophilic reagent. FT-IR curve proved that the aim product was synthesized and the chlorine atom of iron-phosphazene derivative did not completely replaced. The thermal performance of the iron-phosphazene derivative was examined by TGA. This suggests that the iron-phosphazene derivative began to degrade at 200 °C and still has 25 % residue at 700 °C. The residues morphology of the iron-phosphazene derivative was also examined. The surface of residues was smooth, fibrous arrangement and has a certain orientation structure. EDS confirmed that the main components of the higherature calcined residues were C, P and Fe.
- Zhao, Zhengping,Yu, Fengying
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- Ferrocenylalkylation of 2-mercaptobenzoxazoles
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Regioselectivity of the HBF4-catalyzed ferrocenylalkylation of 2-mercaptobenzoxazole in two phase aqueous organic solvent mixture was studied. The reaction proceeds regioselectively at the heterocyclic nitrogen atom. Structures of the synthesiz
- Osipova, E. Yu.,Ivanova,Rodionov,Korlyukov,Arkhipov,Simenel
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- Friedel-crafts acetylation of bis(trimethylsilyl)- and bis(tributylstannyl)ferrocene: implications on the mechanisms of acylation and proton exchange of ferrocene derivatives
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The first unequivocal examples of intermolecular Friedel-Crafts reactions of ferrocene derivatives proceeding via exo attack of the electrophile are reported. Treatment of 1,1′-bis(trimethylsilyl)-(5a) or 1,1′-bis(tributylstannyl)ferrocene (5b) with acetyl chloride in the presence of AlCl3 affords a mixture of three isomeric acetylferrocenes, 1′-acetyl- (6), 2-acetyl-(7), and 3-acetyl-1-(trialkylsilyl and -stannyl)ferrocene (8). Acetylation of 3,3′-dideutero-1,1′-bis(trimethylsilyl)ferrocene (5aD2) under identical conditions generates the corresponding dideuterated products 6aD2-8aD2. Both 6aD2 and 7aD2 contam 1.0 deuterium atom in each cyclopentadienyl ring whereas 8aD2 contains 05 deutenum atom in the substituted ring and 1.5 deuterium atoms in the unsubstituted ring. This demonstrates that the products are formed via exo attack of the electrophile followed by an intramolecular, interannular proton transfer. The lack of scrambling of the deuterium label also suggests that protonation of ferrocenes could also occur through the exo attack of a proton rather than direct protonation at the metal center.
- Cunningham Jr., Allan F.
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- A simple synthetic approach for the transformation of (S)-Ugi's amine
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A simple synthetic approach for the transformation of (S)-Ugi's amine, another configuration of (R)-Ugi's amine, one of the most widely used intermediate in the preparation of chiral ferrocene-based ligands, has been developed via esterification using anhydride, alkaline hydrolysis and active manganese dioxide oxidation, and the corresponding ferrocenyl ketone was afforded in good yields.
- Zha, Gao-Feng,Xu, Wei-Yun,Dai, Peng,Lai, Xiao-Yan,Liu, Wei,Shen, Yong-Cun
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- Novel meso-substituted ferrocene-appended porphyrins: Synthesis, characterization, and electrochemical evaluation
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This paper focuses on the synthesis of the novel ferrocene-appended porphyrin architectures and their zinc metal complexes. Tetraferrocenylporphyrins are a class of organometallic compounds where the porphyrin core is functionalized with a ferrocenyl unit at each of the four meso positions. Tetraferrocenylporphyrin derivatives were synthesized via a direct tetramerization reaction between some ferrocene carboxaldehyde derivatives and pyrrole in the presence of BF3·Et2O as an efficient catalyst. Moreover, a metalation reaction between tetraferrocenylporphyrin derivatives and zinc acetate was applied in the synthesis of related zinc complexes. The structures of the new organometallic compounds were confirmed by Fourier transform infrared spectroscopy (FT-IR), 1H NMR, 13C NMR, UV–vis, and CHNS analyses. The redox-active properties of the synthesized compounds were characterized by cyclic voltammetry (CV) analysis.
- Payami, Elmira,Neshad, Saeed,Aghaiepour, Alireza,Teimuri-Mofrad, Reza
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- METAL-ORGANIC POLYHEDRAL INCLUDING METALLOCENE STRUCTURE AND METHOD FOR PREPARING THE SAME
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Disclosed are a metal-organic polyhedron including a metallocene structure and a method for manufacturing the same. Since the metal-organic polyhedron including the metallocene structure has high porosity and excellent electrical conductivity, when metal-organic polyhedron is used for electrodes such as supercapacitors or secondary batteries and the like, energy density and output characteristics of a device can be improved.
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Paragraph 0136
(2021/06/22)
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- Bismuth subnitrate-catalyzed markovnikov-type alkyne hydrations under batch and continuous flow conditions
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Bismuth subnitrate is reported herein as a simple and efficient catalyst for the atom-economical synthesis of methyl ketones via Markovnikov-type alkyne hydration. Besides an effective batch process under reasonably mild conditions, a chemically intensified continuous flow protocol was also developed in a packed-bed system. The applicability of the methodologies was demonstrated through hydration of a diverse set of terminal acetylenes. By simply switching the reaction medium from methanol to methanol-d4, valuable trideuteromethyl ketones were also prepared. Due to the ready availability and nontoxicity of the heterogeneous catalyst, which eliminated the need for any special additives and/or harmful reagents, the presented processes display significant advances in terms of practicality and sustainability.
- ?tv?s, Sándor B.,Fül?p, Ferenc,Szécsényi, Zsanett
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- Cu2+-selective naked-eye ‘off–on' fluorescent probe with multisignals: chromaticity, fluorescence, electrochemistry
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In this study, a rhodamine–acetylferrocene conjugate of RBFc was synthesized and then characterized using spectroscopy and single-crystal analysis. The chemosensor RBFc exhibited a marked colour change from colourless to pink after binding to Cu2+ ions. Importantly, under the presence of the other competing cations in aqueous solution, only Cu2+ ions caused spirolactam ring opening in rhodamine B in RBFc, resulting in an enhanced absorbance of ultraviolet light spectra and fluorescence spectra, as well as obvious shifts in cyclic voltammetry curves and differential pulsed voltammetry curves. The novel probe described in this manuscript provides an attractive approach for detecting Cu2+ in the presence of other multisignals.
- Xu, Xiuling,Zhang, Xiaoli,Cao, Cuilan,Zheng, Bingbing,Deng, Hongxia,Shuai, Qi
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p. 1142 - 1150
(2020/05/25)
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- Synthesis of ferrocenyl-containing silicone rubbers via platinum-catalyzed Si–H self-cross-linking
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Self-cross-linkable ferrocenyl-containing polymethylhydrosiloxanes were synthesized. Karstedt's catalyst and cis-[PtCl2(BnCN)2] were examined as cross-linking catalysts at room temperature for the reaction between Si–H groups of the ferrocenyl-containing polymethylhydrosiloxanes. Cis-[PtCl2(BnCN)2] is an effective catalyst that allows cross-linked ferrocenyl-containing silicones (silicone rubbers) to be obtained with no visible mechanical defects (bubbles or cracks) compared with Karstedt's catalyst. The ferrocene content of the ferrocenyl-containing silicone rubbers was found to be approximately 50?wt.% by energy-dispersive X-ray analysis. Compared with cross-linked non-modified polymethylhydrosiloxanes, the ferrocenyl-containing silicone rubbers exhibited improved tensile properties (the tensile strength increased from 0.47 to 0.75?MPa) and a 1.5–2.5 times lower cross-linking degree. The surface resistivity of the ferrocenyl-containing silicone rubbers (50?wt.% ferrocenyl units) was approximately 7 × 109?Ω/□, which was 10,000 times lower than that of pure polymethylhydrosiloxane. The obtained flexible electroactive ferrocenyl-containing silicone rubbers can potentially be applied as coatings for electronic and electrostatic-sensitive devices, interfaces, and sensors.
- Deriabin, Konstantin V.,Lobanovskaia, Ekaterina K.,Kirichenko, Sergey O.,Barshutina, Marie N.,Musienko, Pavel E.,Islamova, Regina M.
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- Electronic Asymmetry of an Annelated Pyridyl-Mesoionic Carbene Scaffold: Application in Pd(II)-Catalyzed Wacker-Type Oxidation of Olefins
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The two donor modules of an annelated pyridyl-mesoionic carbene ligand (aPmic) have different σ- and π-bonding characteristics leading to its electronic asymmetry. A Pd(II) complex 1 featuring aPmic catalyzes the oxidation of a wide range of terminal olefins to the corresponding methyl ketones in good to excellent yields in acetonitrile. The catalytic reaction is proposed to proceed via syn-peroxypalladation and a subsequent rate-limiting 1,2-hydride shift, which is supported by kinetic studies. The electronic asymmetry of aPmic renders a well-defined coordination sphere at Pd. The favored arrangement of reactants on the metal center features an olefin trans to the pyridyl module and a tbutylperoxide trans to the carbene. This arrangement gains added stability by the π-delocalization paved by the compatible orbitals on Pd, the pyridyl module, and the olefin that is perpendicular to the Pd(aPmic) plane. The π-interactions are absent in an alternate arrangement wherein the olefin is trans to the carbene. Density functional theory studies reveal the matching orbital overlaps responsible for the preferred arrangement over the other. This work provides an orbital description for the electronic asymmetry of aPmic.
- Bera, Jitendra K.,Dutta, Indranil,Kunnikuruvan, Sooraj,Reshi, Noor U Din,Saha, Sayantani,Yadav, Suman
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p. 11385 - 11393
(2020/11/23)
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- Aminoxyl-Catalyzed Electrochemical Diazidation of Alkenes Mediated by a Metastable Charge-Transfer Complex
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We report the development of a new aminoxyl radical catalyst, CHAMPO, for the electrochemical diazidation of alkenes. Mediated by an anodically generated charge-transfer complex in the form of CHAMPO-N3, radical diazidation was achieved across a broad scope of alkenes without the need for a transition metal catalyst or a chemical oxidant. Mechanistic data support a dual catalytic role for the aminoxyl serving as both a single-electron oxidant and a radical group transfer agent.
- Siu, Juno C.,Parry, Joseph B.,Lin, Song
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supporting information
p. 2825 - 2831
(2019/02/14)
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- Synthesis and Characterization of Diferrocenyl Conjugates: Varying π-Conjugated Bridging Ligands and its Consequence on Electrochemical Communication
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Organometallic wire-like complexes with ferrocenyl termini, conjugated with one and two units of thienylethynyl (M1 and M2) and thienyl (M3 and M4) groups, have been synthesized with a general formula of [Fc-C≡C-(Th-C≡C)1-2-Fc] and [Fc-(Th)1-2-Fc] (Fc = ferrocenyl, Th = thienyl) respectively. The diferrocenyl organometallic complexes have been characterized by various spectroscopic tools such as multinuclear NMR, FTIR, elemental analysis, and mass spectrometry. The electrochemical properties of these compounds have been investigated by cyclic (CV) and differential pulse voltammetry (DPV). The single reversible oxidation wave in diferrocenyl complexes with thienylethynyl spacers (M1 and M2) indicates the absence of intramolecular electrochemical communication between the two ferrocenyl termini. Interestingly, the diferrocenyl complexes with one and two thienyl spacers (M3 and M4) show two successive reversible one-electron oxidation waves, indicating electronic coupling between the two ferrocenyl (Fc) termini. The potential difference (ΔE1/2) between the two redox centers is 160 mV and 130 mV, respectively, with the corresponding comproportionation constants (Kc) of 6.2 × 102 and 1.5 × 102. Upon mono-oxidation of M3 by [Cp2Fe][BF4], a broad and weak intervalence charge-transfer (IVCT) transition is observed in the NIR region of 1200–2200 nm.
- Roy, Sourav Saha,Patra, Sanjib K.
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supporting information
p. 2193 - 2201
(2019/04/17)
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- Aerobic oxidation of alcohols with air catalyzed by decacarbonyldimanganese
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The oxidation of alcohols to carbonyl compounds using air as the terminal oxidant is highly desirable. As described in previous reports, the abstraction of α-H of the alcohol is the most important step, and it typically requires not only a metal catalyst but also complex ligands, co-catalysts and bases. Herein, we report a practical and efficient method for the oxidation of primary alcohols, secondary alcohols, 1,2-diols, 1,2-amino alcohols, and other α-functionalized alcohols using a commercially available catalyst, Mn2(CO)10, and no additives. Preliminary mechanistic studies indicated that an alkoxyl radical intermediate existed in our system, and a plausible mechanism consistent with the experimental results and literature was proposed.
- Meng, Shan-Shui,Lin, Li-Rong,Luo, Xiang,Lv, Hao-Jun,Zhao, Jun-Ling,Chan, Albert S. C.
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supporting information
p. 6187 - 6193
(2019/11/20)
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- Rhodium-Catalyzed Asymmetric Allylation of Malononitriles as Masked Acyl Cyanide with Allenes: Efficient Access to β,γ-Unsaturated Carbonyls
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A rhodium-catalyzed regio- and enantioselective intermolecular allylation of malononitriles as masked acyl cyanides (MAC) with terminal and symmetrical internal allenes is reported. A RhI/Josiphos catalytic system combined with subsequent oxidative degradation of the primary adducts enables a straightforward access to α-branched, β,γ-unsaturated carbonyl compounds. The present protocol exhibits perfect atom economy in the allylation step and is characterized by a great functional group compatibility. Furthermore, the use of α-substituted malononitriles allowed for the construction of all-carbon quaternary centers.
- Grugel, Christian P.,Breit, Bernhard
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supporting information
p. 15223 - 15226
(2018/09/25)
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- Preparation method of (S)-1-ferrocenyl ethanol
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The invention relates to a preparation method of (S)-1-ferrocenyl ethanol. According to the preparation method, ferrocene and acetyl chloride are taken as the raw materials, (S)-1-ferrocenyl ethanol is synthesized after two steps: Friedel-Crafts reactions and asymmetric hydrogenation reduction, the yield is high, and the provided preparation method has the advantages of high yield, low cost, environmental friendliness, easy operation, and suitability for industrialization.
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Paragraph 0025; 0029
(2018/09/11)
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- Design, synthesis and fungicidal activity studies of 3-ferrocenyl-N-acryloylmorpholine
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Ferrocene and its derivatives have been widely used in many fields and also used to modify and improve the performance. Particularly, their low toxicity also attract much attention in medical and pesticide fields. In order to get fungicides with higher biological activity, ferrocenyl groups were introduced into the skeleton of dimethomorph instead of phenyl groups and a series of 3-ferrocenyl-N-acryloylmorpholine were synthesized. The fungicidal bioassay results indicated that most of compounds showed moderate fungicidal activities against 14 kinds of agricultural pathogenic fungi and some compounds displayed higher fungicidal activities than that of dimethomorph. Intrestlingly, compounds 5(Z) exhibited better fungicidal activity against Sclerotinia sclerotiorum than that of compound 5(E).
- Chen, Peiqi,Liu, Chunjuan,Hu, Jianfeng,Zhang, Hao,Sun, Ranfeng
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p. 113 - 121
(2017/12/12)
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- A Practical Three-Step Synthesis of Vinylferrocene
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An improved, short and efficient synthesis of vinylferrocene is reported. This three-step synthesis includes Friedel-Crafts acylation, reduction, and a one-pot mesylation/elimination step to afford the target compound in 62% yield over three steps.
- Plevová, Kristína,Mudráková, Brigita,?ebesta, Radovan
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p. 760 - 763
(2017/12/26)
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- FUNCTIONALIZED MAGNETIC NANOPARTICLE, A CATALYST, A METHOD FOR FORMING C-C BONDS
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A functionalized magnetic nanoparticle including an organometallic sandwich compound and a magnetic metal oxide. The functionalized magnetic nanoparticle may be reacted with a metal precursor to form a catalyst for various C—C bond forming reactions. The catalyst may be recovered with ease by attracting the catalyst with a magnet.
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Paragraph 0194
(2018/04/20)
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- Nitro-imidazoles in ferrocenyl alkylation reaction. Synthesis, enantiomeric resolution and in vitro and in vivo bioeffects
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Ferrocenylalkyl nitro-imidazoles (4a-h, 5a-h) were prepared via the regiospecific reaction of the α-(hydroxy)alkyl ferrocenes, FcCHR (OH) (1a–h; Fc = ferrocenyl; R = H, Me, Et, Pr, i-Pr, Ph, ortho-Cl-Ph, ortho-I-Ph), with nitro-imidazoles in aqueous organic medium (H2O-CH2Cl2) at room temperature in the presence of HBF4, within several minutes in good yields. X-ray structural data for racemic (R,S)-1-N-(benzyl ferrocenyl)-2-methyl-4-nitroimidazole (5f) were determined. The resulting enantiomers were resolved into enantiomers by analytical HPLC on modified amylose or cellulose chiral stationary phases. The viabilities of 4b, 4d, 5b, 5c in vitro, and in experiments in vivo antitumor effects of 1-N-ferrocenylethyl-4-nitroimidazole (4b) against murine solid tumor system Ca755 carcinoma were evaluated.
- Snegur, Lubov V.,Lyapunova, Maria V.,Verina, Daria D.,Kachala, Vadim V.,Korlyukov, Alexander A.,Ilyin, Mikhail M.,Davankov, Vadim A.,Ostrovskaya, Larissa A.,Bluchterova, Natalia V.,Fomina, Margarita M.,Malkov, Victor S.,Nevskaya, Kseniya V.,Pershina, Alexandra G.,Simenel, Alexander A.
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- Hydrogen bond donor solvents enabled metal and halogen-free Friedel–Crafts acylations with virtually no waste stream
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We have developed a metal and halogen-free Friedel–Crafts acylation protocol with virtually no waste stream generation. We propose a hydrogen bonding donor solvent will form a hydrogen bonding network and may provide significant rate enhancement for Friedel–Crafts reactions. Trifluoroacetic acid is one of the strongest H-bond donor solvents, which is also volatile and can be easily recovered by distillation without need for reaction workup. Our protocol is a ‘green’ Friedel–Crafts acylation process: 1) the catalyst can be recovered and reused; 2) using halogen free starting material (carboxylic acids anhydride or carboxylic acids); 3) no need for aqueous reaction work-up; 4) minimum or no waste steam generation.
- Liu, Guangchang,Xu, Bo
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supporting information
p. 869 - 872
(2018/02/09)
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- Design, Synthesis, and Biological Evaluation of Novel 1,3,4-Thiadiazolylpyrazolines Compounds Containing Ferrocene
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The synthesis of 1,3,4-thiadiazole skeleton compounds exhibiting high fungicidal activities has been demonstrated. Thirteen novel 1,3,4-thiadiazolyl-pyrazolines compounds containing ferrocene were designed and synthesized from the ferrocenylchalcones intermediates 3a–3m and the 2-hydrazino-5-phenyl-1,3,4-thiadiazole intermediate 8. All compounds were characterized by 1H NMR, 13C NMR, FT-IR spectra, and HR-MS, and the structure of one of the new compounds N-(4-phenyl-1,3,4-thiadiazol-2-yl)-3-ferrocenyl-5-phenyl-pyrazoline 9a was further determined by X-ray diffraction analysis. The preliminary results of a biological activity assay indicated that all the title compounds exhibited significant fungicidal activities against Pythium solani, Gibberella saubinetii, and Gibberella nicotiancola. Furthermore, compounds 9e and 9h displayed even higher fungicidal activities against the three fungal species compared with the control drug pyraclostrobin.
- Chen, Liqin,Duan, Huihui,Zhang, Xinyu,Zhang, Qiong,Huang, Hailian,Zhao, Junlong,Chen, Bang,Hua, Chengwen,Gou, Xiaofeng
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p. 1978 - 1985
(2018/07/31)
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- Efficient synthesis of ferrocifens and other ferrocenyl-substituted ethylenes: Via a 'sulfur approach'
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Stable and non-odorous alkyl ferrocenyl thioketones react with bis(4-methoxyphenyl)diazomethane according to the 'two-fold extrusion' reaction principles, and tetrasubstituted ethylenes obtained thereby can be demethylated to give (Fc,2OH)-ferrocifens in good yields. The method offers an alternative approach to this class of medically relevant compounds. A similar protocol with alkyl ferrocenyl thioketones and selected diaryldiazomethanes leads to ferrocenyl-substituted ethylenes including dibenzofulvenes. These products are of potential interest for electrochemical and photophysical studies.
- Mlostoń, Grzegorz,Hamera-Fa?dyga, Róza,Celeda, Ma?gorzata,Heimgartner, Heinz
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p. 4350 - 4356
(2018/06/21)
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- Photo induced alkyne hydration reactions mediated by a water soluble, reusable Rhodium (I) catalyst
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Under photochemical irradiation, the hydration of aryl alkynes in the presence of water proceeds in good yields to afford the corresponding ketone, using a water-soluble rhodium (I) catalyst. The catalyst is effective for internal and terminal alkynes and showed high functional group compatibility. A low catalyst loading, low temperature and shorter duration of photolysis are ideal feature of reaction. The catalyst can be reused several times under aerobic and aqueous conditions, exemplifying the robust nature of the catalyst. In comparison with known Rh and other metal catalysts, the present reaction provides a remarkable green approach for alkyne hydration reactions.
- Ali, Munsaf,Srivastava, Avinash K.,Siangwata, Shepherd,Smith, Gregory S.,Joshi, Raj K.
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- Metal/catalyst/reagent free hydration of alkynes up to gram scale under temperature and pressure controlled condition
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A new green water-mediated metal/catalyst/reagent-free methodology for hydration of alkyne is devised. The remarkable yields of various ketones were achieved when alkynes were heated at 150 °C under 11 bar pressure in an autoclave for 14 h in water-methanol solution. Outstanding functional group compatibility for both the terminal and internal alkynes was established. This methodology produces excellent yields up to gram scale under optimised reaction condition.
- Ali, Munsaf,Srivastava, Avinash K.,Joshi, Raj K.
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p. 2075 - 2078
(2018/05/04)
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- Method for preparing ferrocenyl phosphine oxide ligand
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The invention discloses a simple, convenient and quick preparation method for synthesizing a ferrocenyl phosphine oxide ligand. The method comprises the steps of firstly, carrying out a Friedel-Crafts acylation reaction on ferrocene which serves as a starting raw material so as to obtain acyl ferrocene, carrying out a reaction with p-toluenesulfonhydrazide so as to produce a ferrocenyl-containing p-toluenesulfonylhydrazone compound, and carrying out a reaction with a phosphorus oxide containing phosphorus-hydrogen bonds under the catalysis of copper to form a carbon-phosphorus bond, thereby obtaining the ferrocenyl phosphine oxide. According to the method disclosed by the invention, reaction steps are few, the operation is simple and convenient, the yield is high, and the tolerance to functional groups is very good. By the method, ferrocenyl phosphine oxide ligands containing a variety of different substituents can be synthesized.
- -
-
Paragraph 0020; 0034
(2017/10/11)
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- Acetyl ferrocene synthesis method
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The invention discloses an acetyl ferrocene synthesis method, which comprises: (1) mixing acetic anhydride and phosphoric acid, and stirring for 10-15 min at a room temperature; (2) adding a ferrocene solid, heating to a temperature of 35-40 DEG C, and carrying out thermal insulation; (3) heating to a temperature of 45-50 DEG C, and carrying out a reaction until the ferrocene completely reacts; (4) rapidly pouring the reaction solution into crushed ice, adjusting the pH value to 6-7, and filtering to obtain an acetyl ferrocene crude product; and (5) re-crystallizing to obtain the acetyl ferrocene pure product. According to the present invention, the synthesis method has advantages of mild synthesis reaction conditions, easy temperature control, and high yield.
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Paragraph 0021; 0022; 0023; 0024-0029; 0039-0047; 0057-0065
(2018/04/02)
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- alpha-bromo-acetyl ferrocene synthesis method
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The invention discloses an alpha-bromo-acetyl ferrocene synthesis method, which comprises: (1) mixing acetyl ferrocene, N-bromosuccinimide and ethanol, and uniformly stirring; (2) placing the mixture in a microwave oven, adjusting the microwave power to 650-720 W, and carrying out microwave treatment for 4-6 s; (3) supplementing the reaction liquid with ethanol, and carrying out pressure reducing distillation to remove the ethanol to obtain a solid crude product; (4) washing the solid crude product by using petroleum ether, and drying; and (5) carrying out column chromatography separation, and carrying out pressure reducing distillation to obtain alpha-bromo-acetyl ferrocene. Compared to the traditional heating method, the microwave synthesis method of the present invention can remarkably improve the reaction speed of the chemical synthesis, and further has advantages of high reaction selectivity, less side reaction, and high reproducibility.
- -
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Paragraph 0029-0037; 0047-0055; 0065-0073
(2018/04/02)
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- Synthesis method of ferrocenyl pyrimidine polydentate ligand and application thereof in Heck reaction
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The invention discloses a synthesis method of a ferrocenyl pyrimidine polydentate ligand and application thereof in Heck reaction. Ferrocene, pyridine-2-formaldehyde and amidine salt are adopted as the raw materials, and by means of the three-step reaction of acetylation, aldol condensation and condensation cyclization, the ferrocenyl pyrimidine polydentate ligand can be synthesized, the synthesis method has the advantages of simple operation, mild conditions and no use of expensive reagents, and is easy for mass preparation. The invention also relates to application of the ligand in palladium catalyzed Heck coupling reaction. The result shows that the ferrocenyl pyrimidine tridentate ligand 6h has good thermal stability and efficient catalytic activity. The coupling reaction can be carried out under the condition adopting water as the solvent, and the substrate has a wide applicable range, and tedious anhydrous and anaerobic operation is unnecessary.
- -
-
Paragraph 0013-0014; 0023-0025
(2018/03/13)
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- Colchicine metallocenyl bioconjugates showing high antiproliferative activities against cancer cell lines
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A series of ferrocenyl and ruthenocenyl conjugates with colchicine bearing a 1,2,3-triazole moiety were synthesized and their anticancer properties were evaluated. We found that the most potent metallocenyl derivatives Rc4 and Rc5 are 6-7 times more cytotoxic toward HepG2 cells, while Fc4 and Fc5 are two times more cytotoxic toward HCT116 cells as colchicine. We also found that compounds Fc4, Fc5, Rc1 and Rc3-Rc5 are able to induce apoptosis, while compound Fc2 arrests mitosis.
- Kowalczyk, Karolina,B?auz, Andrzej,Ciszewski, Wojciech M.,Wieczorek, Anna,Rychlik, B?azej,Plazuk, Damian
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p. 17041 - 17052
(2017/12/26)
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- Preparation of Bodipy-ferrocene dyads and modulation of the singlet/triplet excited state of bodipy: Via electron transfer and triplet energy transfer
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Modulation of the singlet/triplet excited state of a fluorophore is becoming more important for molecular switches, molecular memory devices, chemical or biological sensors and controllable photodynamic therapy (PDT) etc. Boron-dipyrromethene (Bodipy)-ferrocene (Fc) dyads were prepared for reversible electrochemical switching of the singlet excited state (fluorescence), as well as the triplet excited states of Bodipy. The photophysical properties of the dyads were studied using steady-state UV-vis absorption spectroscopy, fluorescence, electrochemical characterization, time-resolved fluorescence and nanosecond transient absorption spectroscopies. The fluorescence of the Bodipy moieties in the dyads was quenched significantly, due to the photo-induced electron transfer (PET). This conclusion was supported by electrochemical characterization and calculation of the Gibbs free energy changes of PET. We demonstrated that the fluorescence of the Bodipy moiety can be reversibly switched ON and OFF by electrochemical oxidation of the Fc moiety (Fc/Fc+). Furthermore, we proved that the Fc moiety is efficient for quenching of the triplet excited states of Bodipy. Two quenching mechanisms, PET and triplet-triplet-energy transfer (TTET), are responsible for the intramolecular and intermolecular quenching of the triplet excited states of the diiodoBodipy unit.
- Wu, Xueyan,Wu, Wenting,Cui, Xiaoneng,Zhao, Jianzhang,Wu, Mingbo
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supporting information
p. 2843 - 2853
(2016/04/26)
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- A PHOTO-CLEAVABLE MASS TAG AND USE OF THE SAME
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The present invention refers to photo-degradable relates to of the present invention and use thereof markers mass markers mass photo-degradable biomarker-of detecting and quantifying analysis may be utilized, multiple marker synchronous detection of ID. (by machine translation)
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Paragraph 0052; 0054; 0057; 0058
(2016/10/07)
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- Having plant growth-regulating active compound and method for preparing same
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The invention discloses a compound with plant-growth regulating activity. The compound has a structure in a genera formula (I), wherein in the general formula (I), R and R1 are various substituent groups on a benzene ring; R represents a hydrogen atom, alkyl, a fluorine atom, a helium atom, nitryl and trifluoromethyl; R1 represents the hydrogen atom and the fluorine atom, or R and R1 are -CH=CH-CH=CH- and is respectively connected with the second and third bits or the third and fourth bits of the benzene ring. The compound is prepared from ferrocene ethyl ketoxime reacting with substituted benzene isocyanide acid ester. The invention also provides application of the compound as an effective component of a plant growth regulator.
- -
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Paragraph 0033; 0034
(2017/01/31)
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- Magnesium salt promoted tandem nucleophilic addition-Oppenauer oxidation of aldehydes with organozinc reagents
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A magnesium salt promoted synthesis of ketones via tandem nucleophilic addition-Oppenauer oxidation of aldehydes using organozinc chemistry was demonstrated. Magnesium salts concomitantly generated via magnesium metal mediated organohalide zincation exhibit high efficacy for nucleophilic addition of organozinc reagents to aromatic aldehydes and thereafter Oppenauer oxidation whereby ketones are formed in high to excellent yields.
- Fu, Ying,Zhao, Xing Ling,Hügel, Hulmet,Huang, Danfeng,Du, Zhengyin,Wang, Kehu,Hu, Yulai
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supporting information
p. 9720 - 9724
(2016/10/31)
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- Reactions of Cp2TiMe2 with ferrocene and (n5-Cp)Co(n4-C4Ph4) derived esters and amides: A new route for 1-methylvinyl and methyl ketone derived metal sandwich compounds
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Reactions of Cp2TiMe2, with the ester derivatives of organometallic sandwich compounds (n5-RC5H4)Fe(n5-C5H5) and (n5-RC5H4)Co(n4-C4Ph4) (R=ester groups) gave products having R=C(CH2)Me, instead of the expected vinyl ethers indicating conversion of the ester units by Cp2TiMe2 to methyl ketones followed by methylenation. A reaction of Cp2TiMe2 with the diester (n5-RC5H4)Co(n4-C4Ph3R)(R=C(O)OMe) also gave similar results. The study has also been successfully extended to metal sandwich derived amides, thio and seleno esters. By controlling the amount of Cp2TiMe2, the reactions were also stopped at the methyl ketone stage and the methyl ketones were isolated in good yields and characterized. The method provides an easy and direct access to convert organometallic sandwich derived esters and related compounds to 1-methylvinyl derived products.
- Singh, Jatinder,Ghosh, Sanjib,Deb, Mayukh,Elias, Anil J.
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- Enantiopure Ferrocene-Based Planar-Chiral Iridacycles: Stereospecific Control of Iridium-Centred Chirality
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Reaction of [IrCp?Cl2]2 with ferrocenylimines (Fc=NAr, Ar=Ph, p-MeOC6H4) results in ferrocene C-H activation and the diastereoselective synthesis of half-sandwich iridacycles of relative configuration Sp?,RIr?. Extension to (S)-2-ferrocenyl-4-(1-methylethyl)oxazoline gave highly diastereoselective control over the new elements of planar chirality and metal-based pseudo-tetrahedral chirality, to give both neutral and cationic half-sandwich iridacycles of absolute configuration Sc,Sp,RIr. Substitution reactions proceed with retention of configuration, with the planar chirality controlling the metal-centred chirality through an iron-iridium interaction in the coordinatively unsaturated cationic intermediate.
- Arthurs, Ross A.,Ismail, Muhammad,Prior, Christopher C.,Oganesyan, Vasily S.,Horton, Peter N.,Coles, Simon J.,Richards, Christopher J.
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supporting information
p. 3065 - 3072
(2016/03/23)
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- Ruthenium-Catalyzed Enantioselective Hydrogenation of Ferrocenyl Ketones: A Synthetic Method for Chiral Ferrocenyl Alcohols
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Highly effective asymmetric hydrogenation of various ferrocenyl ketones, including aliphatic ferrocenyl ketones as well as the more challenging aryl ferrocenyl ketones, was realized in the presence of a Ru/diphosphine/diamine bifunctional catalytic system. Excellent enantioselectivities (up to 99.8% ee) and activities (S/C = 5000) could be obtained. These asymmetric hydrogenations provided a convenient and efficient synthetic method for chiral ferrocenyl alcohols, which are key intermediates for a variety of chiral ferrocenyl ligands and resolving reagents.
- Lu, Bin,Wang, Qun,Zhao, Mengmeng,Xie, Xiaomin,Zhang, Zhaoguo
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p. 9563 - 9569
(2015/10/12)
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- Synthesis, linear and nonlinear optical properties of thermally stable ferrocene-diketopyrrolopyrrole dyads
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A set of new ferrocene-diketopyrrolopyrrole (Fc-DPP) conjugated dyads was synthesized and their optical, nonlinear optical (NLO) and electrochemical properties were investigated. The second-order nonlinear polarizabilities were determined using hyper-Rayleigh scattering with femtosecond pulsed laser light at 840 nm. The dyads exhibited structure dependent NLO response, which could be explained by correlating optical as well as electrochemical data. In the latter case, it is shown that the amplitude of the Fc based one-electron redox process of D-π-A type dyads is doubled in the dyads of the type D-π-A-π-D, where the acceptor (DPP) is flanked by two Fc donors.
- Kaur, Sarbjeet,Dhoun, Sugandha,Depotter, Griet,Kaur, Paramjit,Clays, Koen,Singh, Kamaljit
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p. 84643 - 84656
(2015/10/28)
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- Variations in the blaise reaction: Conceptually new synthesis of 3-amino enones and 1,3-diketones
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Organic compounds with 3-amino enone or 1,3-diketone functional groups are extremely important, as they can be converted into a plethora of heterocyclic or carbocyclic compounds, or can be used as ligands in metal complexes. We have achieved a new, easy, straightforward and convenient synthesis of 3-amino enones and 1,3-diketones starting from aryl/heteroaryl/alkyl nitriles and 1-aryl/alkyl 2-bromoethanones. The reaction is a variation of the classical Blaise reaction, and it works with zinc and trimethylsilyl chloride as an activator. By running the hydrolysis of the reaction intermediate with HCl (3 N aq.) at 0-30 °C or at 100 °C, it is possible to form either 3-amino enones or 1,3-diketones, respectively. The newly developed method was used for the synthesis of avobenzone, an ingredient of sun-screen lotions. Furthermore, an easy synthesis of (Z)-3-amino-1-[4-(tertbutyl) phenyl]-3-(4-methoxyphenyl)prop-2-en-1-one, with UV/Vis absorption characteristics similar to those of avobenzone, was also achieved.
- Rao, H. Surya Prakash,Muthanna, Nandurka
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supporting information
p. 1525 - 1532
(2015/03/04)
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- Visual detection and removal of mercury ions by a ferrocene derivative
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New ferrocene naphthyridine derivatives were successfully synthesized. The di-substituted ferrocene derivative FecDN behaves as a selective visual chemosensor for mercury ions, exhibiting a rapid and clearly visible precipitation with good selectivity (precipitation) and sensitivity (0.01 μM). The interaction of the ferrocene derivatives and metal ions was investigated by ultraviolet-visible spectroscopy (UV-vis), electrochemical methods, 1H NMR, as well as infrared (IR), and energy dispersive X-ray spectroscopy (EDX). The application of FecDN in the detection and removal of mercury ions is very simple, rapid, and intuitive.
- Peng, Xiaoqian,He, Hanping,Xia, Jingping,Lou, Zhaowen,Chang, Gang,Zhang, Xiuhua,Wang, Shengfu
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p. 3541 - 3544
(2014/06/10)
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- Synthesis and characterization of new ferrocene-containing ionic liquids
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A series of several new families of ferrocene-containing imidazolium salts were synthesized by etherification of ferrocene methanol, acylation of ferrocene, and amide coupling of ferrocene carboxylic acid. The etherification was achieved by an acid-catalyzed procedure and very good yields of between 86-93-% were obtained. Next to the nature of the linkage itself, the lengths of the alkyl chains linking the ferrocenyl moiety and the imidazolium group and the nature of the counterions were also varied. Interestingly, a γ-effect can be observed for the ether compounds but this effect was only visible in 13C NMR spectroscopy. These new redox-active ionic liquids were fully characterized by FTIR, 1H, 19F, and 13C NMR spectroscopy, and by MS, HRMS and elemental analysis. A novel series of ferrocenated ionic liquids with different spacer species between the ferrocenyl moiety and the imidazolium group have been developed. The spacer units have been established by amide coupling, etherification and acylation. The latter reaction is strongly influenced by the chain length of the acid chloride and a γ-effect is observable for the ether compounds. Copyright
- Gharib, Bhasem,Hirsch, Andreas
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p. 4123 - 4136
(2014/07/08)
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- 1-Acetylferroceneoxime-based photoacid generators: Application towards sol-gel transformation and development of photoresponsive polymer for controlled wettability and patterned surfaces
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A newsworthy class of carboxylate and sulfonate esters of 1-acetylferroceneoxime has been demonstrated as non-ionic photoacid generators (PAGs). PAGs based on 1-acetylferroceneoxime were synthesized in good yields by simple treatment of 1-acetylferroceneoxime with various carboxylic and sulfonyl chlorides. Newly developed PAGs of 1-acetylferroceneoxime showed good absorbance >350 nm. On irradiation using UV light (≥365 nm), carboxylates and sulfonates of 1-acetyl ferroceneoxime in aqueous acetonitrile solvent underwent efficient homolytic cleavage of N-O bond, resulting in the generation of carboxylic and sulphonic acids, respectively, with high chemical and good quantum yields. Further, we demonstrated the application of our newly developed 1-acetylferroceneoxime-based PAGs for gelation of biopolymer alginate on UV irradiation. More interestingly, we synthesized a ferroceneoxime bound photoresponsive polymer, 1-acetylferroceneoxime-polycaprolactone (AFO-PCL), and demonstrated its controlled surface wettability and generation of patterned surfaces.
- Ikbal, Mohammed,Banerjee, Rakesh,Barman, Shrabani,Atta, Sanghamitra,Dhara, Dibakar,Singh, N.D. Pradeep
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p. 4622 - 4630
(2014/06/09)
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- Hypervalent iodine mediated direct one pot transformation of aldehydes to ketones
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An environmentally benign, step economical synthesis of ketones directly from aldehydes has been developed using hypervalent iodine as an oxidant. The key features of this protocol are its mild conditions without the use of any heavy and toxic metals for the synthesis of a wide range of ketones. the Partner Organisations 2014.
- Sagara, Prateep Singh,Chebolu, Rajesh,Bahuguna, Ashish,Ravikumar
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p. 15011 - 15013
(2014/04/17)
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