- Anionic thia-fries rearrangements of electron-rich ferrocenes and the unanticipated formation of diferrocenyl sulfate from 2-(trimethylsilyl) ferrocenyl imidazolylsulfonate
-
Upon ortho lithiation ferrocenyl triflate and 1,1′-ferrocenediyl ditriflate undergo anionic thia-Fries rearrangements instead of triflate elimination. To differentiate between an ortho metalation and an ortho deprotonation, 2-(trimethylsilyl)ferrocenyl triflate was shown to undergo an anionic thia-Fries rearrangement to 2-((trifluoromethyl)sulfonyl)ferrocenol (5) in 84% yield upon treatment with tetrabutylammonium fluoride. Metalation of the respective tributylstannyl derivative with butyllithium also led to 5 in 99% yield as the result of the anionic thia-Fries rearrangement. 2-Methoxyferrocenyl triflate also underwent the rearrangement upon ortho deprotonation with lithium diisopropylamide in practically quantitative yield at low temperature. The electron-rich 2-(((trifluoromethyl)sulfonyl)oxy)ferrocenolate was generated from 2-(((trifluoromethyl)sulfonyl)oxy)ferrocenyl acetate. However, ortho deprotonation again afforded the anionic thia-Fries rearrangement product. These results clearly show that even very electron rich ferrocene derivatives undergo an anionic thia-Fries rearrangement instead of a triflate elimination. In an attempt to induce an elimination supported by steric crowding, 2,3,4-trimethylferrocenyl triflate was deprotonated, giving 3,4,5-trimethyl-2- ((trifluoromethyl)sulfonyl)ferrocenol in quantitative yield as the result of an anionic thia-Fries rearrangement. As an alternative to the triflates ferrocenyl imidazolylsulfonate was tested as the starting material. While this compound could not be deprotonated, the corresponding 2-trimethylsilyl derivative reacted with tetrabutylammonium fluoride in a very unusual reaction to give diferrocenyl sulfate in almost quantitative yield.
- Werner, Georg,Butenschoen, Holger
-
-
Read Online
- From 2- to 3-Substituted Ferrocene Carboxamides or How to Apply Halogen dance to the Ferrocene Series
-
Two methods were compared to convert ferrocene into N,N-diisopropylferrocenecarboxamide, N,N-diethylferrocenecarboxamide, N,N-dimethylferrocenecarboxamide, and (4-morpholinocarbonyl)ferrocene, namely, deprotometalation followed by trapping using dialkylcarbamoyl chlorides and amide formation from the intermediate carboxylic acid. The four ferrocenecarboxamides were functionalized at C2 in the case of the less hindered and more sensitive amides, recourse to a mixed lithium-zinc 2,2,6,6-tetramethylpiperidino-based base allowed us to achieve the reactions. Halogen migration using lithium amides was next optimized. Whereas it appeared impossible to isolate the less hindered 3-iodoferrocenecarboxamides, 3-iodo-N,N-diisopropylferrocenecarboxamide proved stable and was converted to new 1,3-disubstituted ferrocenes by Suzuki coupling or amide reduction. DFT calculations were used to rationalize the results obtained.
- Tazi, Mehdi,Erb, William,Halauko, Yury S.,Ivashkevich, Oleg A.,Matulis, Vadim E.,Roisnel, Thierry,Dorcet, Vincent,Mongin, Florence
-
-
Read Online
- Synthesis and structure of novel chiral oxazolinylferrocenes and oxazolinylferrocenylphosphines, and their rhodium(I) -complexes
-
A variety of chiral oxazolinylferrocenes are prepared from either ferrocenecarboxylic acid or cyanoferrocene and chiral β-amino alcohols. Highly diastereoselective ortho-lithiation (84 ～ 99% de) of the oxazolinylferrocenes is accomplished with sec-butyllithium and the treatment of the lithiated compounds with an electrophile such as MeI, Ph2PCI or (PhSe)2 gives the corresponding ortho-substituted oxazolinylferrocenes. The molecular structure of (S,S)-[2-(4′-isopropyloxazolin-2′-yl)ferrocenyl]diphenylphosphine (10), (S,S)-2-phenylseleno-1-(4′-isopropyloxazolinyl)ferrocene (17), (S,R)-3-methyl-1-diphenylphosphino-2-(4′-isopropyloxazolinyl)ferrocene (18), and (S,S,S)-[2-(4′,5′-diphenyloxazolin-2′-yl)ferrocenyl]diphenylphosphine ((S,S,S)-DIPOF; 21) has been fully characterized by X-ray crystallography. In connection with their usefulness as chiral ligands for Rh(I)-catalyzed asymmetric hydrosilylation of ketones, the square planar transition metal complexes having oxazolinylferrocenylphosphines, such as [Rh(COD)(P-N)]BF4 and Rh(CO)(P-N)Cl (P-N = 10 or 21), are prepared by treatment of [Rh(COD)2]BF4 and [Rh(CO)2Cl]2 with 10 and 21, respectively, and all structures have been characterized spectroscopically and further confirmed by X-ray crystallography.
- Nishibayashi, Yoshiaki,Segawa, Kyohei,Arikawa, Yasuyoshi,Ohe, Kouichi,Hidai, Masanobu,Uemura, Sakae
-
-
Read Online
- Independent Quantification of Electron and Ion Diffusion in Metallocene-Doped Metal-Organic Frameworks Thin Films
-
The chronoamperometric response (I vs t) of three metallocene-doped metal-organic frameworks (MOFs) thin films (M-NU-1000, M = Fe, Ru, Os) in two different electrolytes (tetrabutylammonium hexafluorophosphate [TBAPF6] and tetrabutylammonium tetrakis(pentafluorophenyl)borate [TBATFAB]) was utilized to elucidate the diffusion coefficients of electrons and ions (De and Di, respectively) through the structure in response to an oxidizing applied bias. The application of a theoretical model for solid state voltammetry to the experimental data revealed that the diffusion of ions is the rate-determining step at the three different time stages of the electrochemical transformation: an initial stage characterized by rapid electron diffusion along the crystal-solution boundary (stage A), a second stage that represents the diffusion of electrons and ions into the bulk of the MOF crystallite (stage B), and a final period of the conversion dominated only by the diffusion of ions (stage C). Remarkably, electron diffusion (De) increased in the order of Fe 6 1- as the counteranion in all the stages of the voltammogram, demonstrating the strategy to modulate the rate of electron transport through the incorporation of rapidly self-exchanging molecular moieties into the MOF structure. The De values obtained with larger TFAB1- counteranion were generally in agreement with the previous trend but were on average lower than those obtained with PF6 1-. Similarly, the ion diffusion coefficient (Di) was generally higher for TFAB1- than for PF6 1- as the ions diffuse into the crystal bulk, due to the high degree of ion-pair association between PF6 1- and the metallocenium ion, resulting in a faster penetration of the weakly associated TFAB1- anion through the MOF pores. These structure-function relationships provide a foundation for the future design, control, and optimization of electron and ion transport properties in MOF thin films.
- Celis-Salazar, Paula J.,Cai, Meng,Cucinell, Clark A.,Ahrenholtz, Spencer R.,Epley, Charity C.,Usov, Pavel M.,Morris, Amanda J.
-
-
Read Online
- Synthesis and Structure of Planar Chiral, Bifunctional Aminoboronic Acid Ferrocene Derivatives
-
N,N′-Diisopropylferrocenecarboxamide is utilized for an asymmetric, directed metalation approach to several planar chiral bifunctional ferrocene derivatives. Directed metalation using n-butyllithium-(-)-sparteine on N,N′-diisopropylferrocenecarboxamide can be achieved to give high yields of the corresponding boronic acid; however, it was found that a sequence involving asymmetric directed metalation-bromination, followed by lithium-halogen exchange, was more convenient to access the same derivatives since this allowed straightforward determination of the enantiomeric excess. (pR)-2-[(N,N′-Diisopropylamino)methyl]ferrocenylboronic acid and derivatives thereof could be readily accessed with high enantiomeric excess, followed by amide reduction.
- Batsanov, Andrei S.,Herault, Damien,Howard, Judith A. K.,Patrick, Leonard G. F.,Probert, Michael R.,Whiting, Andrew
-
-
Read Online
- Chiral and Redox-Active Room-Temperature Ionic Liquids Based on Ferrocene and l-Proline
-
The syntheses of room-temperature ionic liquids (RTILs) combining the naturally occurring amino acid l-proline and ferrocene (Fc) building blocks are reported. After quaternization of ({[(2S)-N-methylpyrrolidine-2-yl]methyleneoxy}carbonyl)ferrocene (1) with alkyl iodides and anion exchange, the resulting diastereomeric (1S,2S)- and (1R,2S)-[(ferrocenylcarbonyl)oxy]methylene-N,N-dialkylpyrrolidine-1-ium RTILs are redox-active and air- and water-stable. They are also thermally stable up to 263 °C. The electrochemical FeII/FeIIIpotential is shifted to +0.28 V versus Fc/Fc+. Before anion exchange, several iodide derivatives were obtained as crystalline products, and their crystal structures are reported. According to the NMR spectroscopic data cation–anion aggregates are present in the non-coordinating solvent CDCl3. In contrast, in the polar solvent [D6]dimethyl sulfoxide ([D6]DMSO), the ion pairs are separated.
- Bouvet, Carola B.,Krautscheid, Harald
-
-
Read Online
- Synthesis, spectroscopy, electrochemistry and DFT of electron-rich ferrocenylsubphthalocyanines
-
A series of novel ferrocenylsubphthalocyanine dyads Y-BSubPc(H)12 with ferrocenylcarboxylic acids Y-H = (FcCH2CO2-H), (Fc(CH2)3CO2-H) or (FcCO(CH2)2CO2-H) in the axial position were synthesized from the parent Cl-BSubPc(H)12 via an activated triflate-SubPc intermediate. UV/Vis data revealed that the axial ferrocenyl-containing ligand did not influence the Q-band maxima compared to Cl-BSubPc(H)12. A combined electrochemical and density functional theory (DFT) study showed that Fe group of the ferrocenyl-containing axial ligand is involved in the first reversible oxidation process, followed by a second oxidation localized on the macrocycle of the subphthalocyanine. Both observed reductions were ring-based. It was found that the novel Fc(CH2)3CO2BSubPc(H)12 exhibited the lowest first macrocycle-based reduction potential (-1.871Vvs. Fc/Fc+) reported for SubPcs till date. The oxidation and reduction values of Fc(CH2)nCO2BSubPc(H)12 (n = 0-3), FcCO(CH2)2CO2BSubPc(H)12, and Cl-BSubPc(H)12 illustrated the electronic influence of the carboxyl group, the different alkyl chains and the ferrocenyl group in the axial ligand on the ring-based oxidation and reduction values of the SubPcs.
- Conradie, Jeanet,Swarts, Pieter J.
-
-
Read Online
- Ferrocenecarboxylic acid and microwave-assisted synthesis of ferrocenoyl hydrazones
-
A protocol to access ferrocenecarboxylic acid via carboxylation of ferrocene with carbon dioxide in the presence of aluminum chloride was elaborated. An efficient microwave-assisted synthesis of ferrocenoyl hydrazones by condensation of ferrocene carbohydrazide with carbonyl compounds was developed. Structures of the synthesized compounds were examined by NMR spectroscopy and mass spectrometry. Structures of N′-(4-chlorobenzylidene)ferrocenecarbohydrazide, N′-(4-methoxybenzylidene)ferrocenecarbohydrazide, and N′-(2-hydroxybenzylidene)ferrocenecarbohydrazide were determined by X-ray diffraction analysis. Synthesized compounds were found to have no toxicity against P. aeruginosa, E. coli, S. aureus, B. subtilis, M. rubrum, and C. albicans.
- Kulikov,Nikulin,Arkhipov,Rodionov,Babusenko,Kovalenko,Belousov, Yu. A.
-
-
Read Online
- Carbon-Rich Trinuclear Octamethylferrocenophanes
-
Several trinuclear ferrocenes are obtained by Friedel-Crafts reaction of octamethylferrocene with ferrocenoyl chloride and subsequent modifications. 1,1′-Diferrocenoyloctamethylferrocene (3) is transformed to the divinyl derivative (4a) by reaction with MeLi and AlCl3. The reactive 4a cyclizes spontaneously to a [4]ferrocenophane with buta-1,3-diene handle (5) or in the presence of AlCl3 to a [3]ferrocenophane with propene handle (6). Structure assignments are supported by X-ray crystallography and NMR spectroscopy, and mechanisms are proposed. Electrochemical behavior of the compounds was investigated with cyclic voltammetry, and assignments of the redox processes were carried out with the aid of density functional theory calculations. The synthesized compounds and demonstrated transformations represent useful tools for preparation of materials for charge-transport studies in metal-molecule-metal junctions.
- Roemer, Max,Wild, Duncan A.,Sobolev, Alexandre N.,Skelton, Brian W.,Nealon, Gareth L.,Piggott, Matthew J.,Koutsantonis, George A.
-
-
Read Online
- Reduction of Escherichia coli ribonucleotide reductase subunit R2 with eight water-soluble ferrocene derivatives
-
Water soluble ferrocenes [Fe(Cp)(CpL)], where Cp- is the η5-cyclopentadienide ligand and the side chain L is (a) the carboxylic acid group -(CH2)xCO2H with x=0-4 (I-V); (b) the complex x=2 with the β-methylene mono-methyl substituted (VI); (c) the amine hydrochloride derivative with L=CH(Me) NH3+ (VII); and (d) the complex with two Cp rings bridged by the amine hydrochloride -CH(NH3+)CH2CH2- (VIII); have been prepared, and are used as one-equivalent reductants for the active-R2 subunit of Escherichia coli ribonucleotide reductase. Formal reduction potentials E1°′ (25°C) of the carboxylates of acids I-VI in 20 mM NaOH, and of the amine hydrochlorides VII and VIII in water were determined by cyclic voltammetry, and are in the range 0.308-0.550 V versus nhe, I=0.100 M (NaCl). Second-order rate constants k12 (25°C) for the reduction of active-R2 were determined by UV-Vis spectrophotometry, and are in the range 0.15-0.50 M-1 s-1 at I=0.100 M. A free-energy plot of logk12 versus E°′ values gives no clearcut unidirectional trend. Since from present information the electron self-exchange rate constant for the [Fe(Cp)2]+/[Fe(Cp)2] couple is favourable (>7×106 M-1 s-1 in methanol at 25°C), it would appear that electron-transfer from the ferrocenes via Trp-48, Asp-237, His-118 to the FeIII2 site on R2 is much slower than expected, and smaller than with the organic radical reductants previously studied. Electron-transfer from some other position on the protein surface to the Tyr· is considered as an alternative.
- Liu, Aimin,Leese, David N.,Swarts, Jannie C.,Sykes
-
-
Read Online
- Practical Chromatography-Free Synthesis of 2-Iodo- N, N -diiso propylferrocenecarboxamide and Further Transformations
-
An efficient procedure able to deliver grams of racemic and enantioenriched 2-iodo- N, N -diisopropylferrocenecarboxamide without chromatographic purification was developed. To introduce the halogen, two procedures, one using the n BuLi-TMEDA chelate and one using a lithium amide in the presence of ZnCl 2 as in situ trap were developed. Further functionalization by Suzuki-Miyaura and Ullman-type cross-couplings was investigated to access a variety of ferrocene derivatives.
- Dorcet, Vincent,Erb, William,Roisnel, Thierry
-
-
Read Online
- Visual detection and removal of mercury ions by a ferrocene derivative
-
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
-
-
Read Online
- A convenient method for synthesis of novel alkylferrocene derivatives with various functional groups: synthesis, characterization and electrochemical investigation
-
Abstract: In this research, new ferrocenylmethylesters were synthesized according to esterification reaction. To reach this purpose, direct and indirect esterification methods were used. Indirect method included Cannizzaro reaction of new alkylferrocenecarboxaldehydes result in production of alkylferrocenecarboxylic acids and alkyl(hydroxymethyl)ferrocene derivatives. Finally, a variety of known procedures were used for converting the new alkylferrocenecarboxylic acids to the corresponding esters. The oxidative esterification reaction was accomplished using K2CO3/I2 as oxidant in the direct method. The advantages of this method are one-pot and single-step reaction and remarkably high total yield of this procedure. The chemical structures were confirmed with FT-IR, 1H NMR, 13C NMR and MASS spectroscopy as well as CHN analysis. Electrochemical behavior of synthesized compounds was studied by cyclic voltammetry, and the relationship between the peak currents and the square root of the scan rate showed that the redox process is diffusion-limited. Graphic abstract: [Figure not available: see fulltext.].
- Teimuri-Mofrad, Reza,Aghaiepour, Alireza,Rahimpour, Keshvar
-
p. 2449 - 2462
(2020/05/06)
-
- Ferrocenyl Janus mixed-dendron stars and their stabilization of Au and Ag nanoparticles
-
Janus molecular architectures have recently attracted attention due to their structures and properties that differ from those of traditional symmetric structures. Herein, two new small redox-reversible mixed-dendron star-shape molecules containing three ferrocenyl groups have been synthesized by linking two distinct dendrons using an esterification reaction. These organometallic nano structures were characterized by 1H and 13C NMR, MS, IR and UV–vis. spectroscopies and cyclic voltammetry confirming the number of ferrocenyl groups and AFM and DLS showing micellar assemblies. Au and Ag nanoparticles were stabilized in the presence of a mixed-dendron structure having amidoferrocene termini upon reaction of the nanoparticle metal precursor with NaBH4. Compared reactions of the two star-molecules with HAuCl4 showed a slow redox reaction leading to Au nanoparticles only with the star-molecule terminated with triazolyferrocene termini, which is taken into account by the difference of their redox potentials.
- Liu, Yue,Mu, Shengdong,Liu, Xiong,Ling, Qiangjun,Hang, Chaodong,Ruiz, Jaime,Astruc, Didier,Gu, Haibin
-
supporting information
p. 4777 - 4789
(2018/07/31)
-
- Bis(methoxypropyl) ether-promoted oxidation of aromatic alcohols into aromatic carboxylic acids and aromatic ketones with O2 under metal- and base-free conditions
-
We describe an eco-friendly, practical and operationally simple procedure for the bis(methoxypropyl) ether-promoted oxidation of aromatic alcohols into aromatic carboxylic acids and aromatic ketones with atmospheric dioxygen as the sole oxidant. This chemical process is clean with high conversion and good selectivity, and an external initiator, catalyst, additive and base are not required. The virtue of this reaction is highlighted by its easily available and economical raw materials and excellent functional group tolerance (acid-, base- and oxidant-labile groups).
- Liu, Kai-Jian,Jiang, Si,Lu, Ling-Hui,Tang, Ling-Li,Tang, Shan-Shan,Tang, Hai-Shan,Tang, Zilong,He, Wei-Min,Xu, Xinhua
-
supporting information
p. 3038 - 3043
(2018/07/13)
-
- Synthetic method for ferrocenecarboxylic acid based on supercritical carbon dioxide liquid
-
The invention provides a synthetic method for ferrocenecarboxylic acid based on supercritical carbon dioxide liquid. The synthetic method comprises the following steps that aluminum trichloride is added into a solvent under an ice bath environment and is heated to be completely dissolved, then carbon nano tubes are added, and full stirring is carried out so as to obtain an aluminum-trichloride-loaded carbon nano tube catalyst; ferrocene is dissolved in toluene, after ferrocene is fully dissolved, ferrocene is transferred into a supercritical device, supercritical carbon dioxide fluid is introduced, the aluminum-trichloride-loaded carbon nano tube catalyst is slowly added in the slow heating process, constant-temperature reaction is carried out, strong acid is added, ice bath hydrolysis iscarried out, and filtration is carried out so as to obtain a ferrocenecarboxylic acid crude product; and extraction is carried out on the ferrocenecarboxylic acid crude product by using toluene, thenlow-temperature constant-temperature refrigeration purification treatment is carried out, and then melting is carried out so as to obtain ferrocenecarboxylic acid. According to the synthetic method, the multi-walled carbon nanotube reinforced aluminum oxide catalyst is obtained, the supercritical carbon dioxide fluid replaces carbon dioxide gas, so that the reaction is more low-temperature and efficient, the controllability is high, the reaction efficiency is improved, and the yield and the purity of a product are also obviously improved.
- -
-
Paragraph 0024-0056
(2018/11/04)
-
- Design, synthesis and fungicidal activity studies of 3-ferrocenyl-N-acryloylmorpholine
-
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
-
p. 113 - 121
(2017/12/12)
-
- Ferrocene-based retinoic acid/paclitaxel nano particles with targeting function on tumor cells and application thereof
-
The invention discloses ferrocene-based retinoic acid/paclitaxel nano particles with a targeting function on tumor cells and application thereof in preparation of medicine for treating tumors, and belongs to the technical field of nano medicine. The prepared nano particles keep retinoic acid, tumor stem cell hyperplasia is inhibited, differentiation activity is induced, meanwhile, paclitaxel is carried, and the function of killing common tumor cells except for tumor stem cells can be achieved. The nano particles are sensitive to high-concentration reduced glutathione in the tumor cells, the nano particles can be fast dissociated to release paclitaxel after entering the tumor cells, the function group of retinoic acid is exposed, and therefore the function is achieved. Due to the fact that the reduced glutathione content in normal cells is small, no paclitaxel is released, or a little paclitaxel is released, the toxic effect on the normal cells is reduced. Meanwhile, the nano particles can carry and transfer Micro-RNA to enter the cells to achieve the corresponding function, and therefore the nano particles can be used for preparing the medicine for treating the tumors.
- -
-
Paragraph 0021-0023
(2017/06/24)
-
- Highly Enantioselective Ferrocenyl Palladacycle-Acetate Catalysed Arylation of Aldimines and Ketimines with Arylboroxines
-
Benzylic N-substituted stereocenters constitute a frequent structural motif in drugs. Their highly enantioselective generation is hence of technical importance. An attractive strategy is the arylation of imines with organoboron reagents. Chiral Rh complexes have reached a high level of productivity for this reaction type. In this article we describe that an electron rich PdIIcatalyst also performs well in the arylation of aldimines, comparable to the best Rh catalysts. The ferrocenyl palladacycle-acetate catalyst allows for a broad substrate scope and very high enantioselectivities. Commonly observed side reactions like aryl–aryl homocouplings and imine hydrolysis could be blocked. Mechanistic studies implicate that a) the acetate ligand is crucial for transmetallation, b) the active catalyst is most likely a palladacycle-OAc monomer, c) the rate limiting step is probably the product release. By added KOAc the arylation could also be applied to ketimines.
- Schrapel, Carmen,Frey, Wolfgang,Garnier, Delphine,Peters, René
-
supporting information
p. 2448 - 2460
(2017/02/23)
-
- A Strained Disilane-Promoted Carboxylation of Organic Halides with CO2 under Transition-Metal-Free Conditions
-
By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency.
- Mita, Tsuyoshi,Suga, Kenta,Sato, Kaori,Sato, Yoshihiro
-
supporting information
p. 5276 - 5279
(2015/11/18)
-
- Organometallic 2-cyano-2-aminobenzoate-propyl derivates and their use as anthelmintics
-
The invention relates to compounds characterized by a general formula (1), wherein X is a group described by a general formula -Kp-Fl- Kq-, wherein - Fl is -C(=O)-,-C(=S)-, with I being 0 or 1, - Kp is a Cp-alkyl with p being 0, 1, 2, 3 or 4, - Kq is a Cq-alkyl with q being 0, 1, 2, 3 or 4, and wherein n of R1n is 0, 1, 2, 3, 4 or 5, and each R1 independently from any other R1 is -C(=O)OR2, -C(=O)NR22, -C(=O)SR2, -C(=S)OR2, -C(NH)NR22, CN4H2, -NR22, -C(=O)R2, -C(=S)R2, -OR2, -SR2, -CF3, -OCF3, -SCF3, -SOCF3, -SO2CF3, -CN, -NO2, -F, -Cl, -Br or -I, with each R2 independently from any other R2 being a hydrogen or C1-C4 alkyl, and wherein OM is an organometallic compound independently selected from the group of an unsubstituted or substituted metal sandwich compound, an unsubstituted or substituted half metal sandwich compound or a metal carbonyl compound and their use in a method for treatment of infections by helminths.
- -
-
Paragraph 0119
(2015/01/18)
-
- BIS-ORGANOMETALLIC 2-AMINO-3-HYDROXY-2-METHYLPROPANENITRILE DERIVATIVES FOR USE AS ANTHELMINTICS
-
The invention comprises a compound characterized by a general formula (1), wherein X is a group described by a general formula -Kp-Fl-Kq-, wherein - Fl is -C(=O)-,-C(=S)-,with l being 0 or 1, - Kp is a Cp–alkyl with p being 0, 1, 2, 3 or 4, - Kq is a Cq-alkyl with q being 0, 1, 2, 3 or 4, and wherein Z is a group described by a general formula –Kr-Fi–Kt-, wherein - Fi is -O-, -S-, -O-C(=O)-, -O-C(=S)-, -S-C(=O)- or NH-(C=O)-with i being 0 or 1, - Kr is a Cr-alkyl with r being 0, 1, 2, 3 or 4, - Kt is a Ct-alkyl with t being 0, 1, 2, 3 or 4, wherein each OM is an organometallic compound independently selected from each other from the group of an unsubstituted or substituted metal sandwich compound, an unsubstituted or substituted half metal sandwich compound or a metal carbonyl compound and their use.
- -
-
Page/Page column 31; 32
(2015/04/15)
-
- ORGANOMETALLIC N-2-CYANO-1-HYDROXYPROPAN-2-YL FOR USE AS ANTHELMINTICS
-
The invention relates to a compound characterized by a general formula (1), wherein OM is an organometallic compound independently selected from the group of an unsubstituted or substituted metal sandwich compound, an unsubstituted or substituted half metal sandwich compound or a metal carbonyl compound, wherein Z is a group described by a general formula –Kr-Fi–Kt-, wherein -Fi is -O-, -S-, -O-C(=O)-, -O-C(=S)-, -S-C(=O)- or NH-(C=O)- with i being 0 or 1, -Kr is a Cr-alkyl with r being 0, 1, 2, 3 or 4, -Kt is a Ct-alkyl with t being 0, 1, 2, 3 or 4, and wherein each RX1 independently from any other RX1 is -C(=O)ORX2, -C(=O)NRX22, -C(=O)SR X2, -C(=S)OR X2, -C(NH)NR X22, CN 4 H 2, -NR X22,-C(=O)R X2, -C(=S)R X2, -OR X2, -SR X2, -CF 3,-OCF 3, -SCF 3, -SOCF 3, -SO 2 CF 3,-CN, -NO 2, -F, -Cl, -Br or -I, and wherein - n of R X1n is 0, 1, 2, 3, 4 or 5, and with each R X2 independently from any other R X2 being hydrogen or an unsubstituted or substituted C1 -C 4 alkyl and their use in a method for treatment of infections by helminths.
- -
-
Page/Page column 30-32
(2015/04/15)
-
- ORGANOMETALLIC 2-CYANO-2-AMINOBENZOATE-PROPYL DERIVATES AND THEIR USE AS ANTHELMINTICS
-
The invention relates to compounds characterized by a general formula (1), wherein X is a group described by a general formula -Kp-Fr Kq-, wherein - Fl is -C(=0)-,-C(=S)-, with I being 0 or 1, - Kp is a Cp-alkyl with p being 0, 1, 2, 3 or 4, - Kq is a Cq -alkyl with q being 0, 1, 2, 3 or 4, and wherein n of R1n is 0, 1, 2, 3, 4 or 5, and each R1 independently from any other R1 is -C(=O)OR2, -C(=O)NR22, -C(=O)SR2, -C(=S)OR2, -C(NH)NR22, CN4H2, -NR22, -C(=O)R2, -C(=S)R2, -OR2, -SR2, -CF3, -OCF3, -SCF3, -SOCF3, -SO2CF3, -CN, -NO2, -F, -CI, -Br or -I, with each R2 independently from any other R2 being a hydrogen or C1-C4 alkyl, and wherein OM is an organometallic compound independently selected from the group of an unsubstituted or substituted metal sandwich compound, an unsubstituted or substituted half metal sandwich compound or a metal carbonyl compound and their use in a method for treatment of infections by helminths.
- -
-
Page/Page column 36
(2015/01/16)
-
- Synthesis and characterization of new ferrocene-containing ionic liquids
-
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
-
supporting information
p. 4123 - 4136
(2014/07/08)
-
- Direct carboxylation of simple arenes with CO2 through a rhodium-catalyzed C-H bond activation
-
Direct carboxylation of simple arenes under atmospheric pressure of CO2 is achieved through a rhodium-catalyzed C-H bond activation without the assistance of a directing group. Various arenes such as benzene, toluene, xylene, electron-rich or electron-deficient benzene derivatives, and heteroaromatics are directly carboxylated with high TONs. This journal is
- Suga, Takuya,Mizuno, Hajime,Takaya, Jun,Iwasawa, Nobuharu
-
supporting information
p. 14360 - 14363
(2015/02/19)
-
- Nano islet formation of formyl- and carboxyferrocene, -ruthenocene, -osmocene and cobaltocenium on amine-functionalized silicon wafers highlighted by crystallographic, AFM and XPS studies
-
Surface-hydroxylated silicon wafers, 8, were reacted with 3-aminopropyltrimethoxysilane, 9, to create wafers with amine-functionalized surfaces, 10. The metallocenylaldehydes FcCHO, 1 (Fc = ferrocenyl = Fe II(C5H5)(C5H4)), RcCHO, 2 (Rc = ruthenocenyl = RuII(C5H5)(C 5H4)), and OcCHO, 3 (Oc = osmocenyl = Os II(C5H5)(C5H4)) as well as the carboxylic acids FcCOOH, 4, RcCOOH, 5, OcCOOH, 6, and Cc +COOH·PF6-, 7 (Cc+ = cationic cobaltocenium = [CoIII(C5H5)(C 5H4)]+), were reacted with 10 to covalently anchor the metallocenes on the wafers either via an imine (-CHN-) or amide (-NHCO-) bond. The aldehydes were anchored more effectively than the carboxylic acids. Binding energies of all important atoms in all seven systems were determined by XPS measurements. Metal binding energies of the amide-bonded metallocenes were consistently larger (up to 0.6 eV) than those of the imine-anchored systems. AFM and SEM measurements showed that the covalently anchored metallocenes aggregate into nano-islets of diameter between 40 and 100 nm depending on the metallocene and type of anchoring bond. Up to seven additional layers of unreacted metallocenylaldehyde or -acid further stacked on top of the main layer of metallocene to form each islet. These additional layers of metallocene of each islet are stabilized by a large network of secondary and/or tertiary bonding forces. The main film surfaces have average thicknesses ranging between 2 and 6 nm, while film roughness, which is mostly associated with the islets, was with one exception (that of the Oc-CONH- surface 14) between 17% and 68% of the film thickness. The crystal structures for OcCHO, 3, and Cc+COOH·PF6-, 7, was determined and the observed tertiary and secondary intermolecular interactions between independent molecules explains the formation of the nano-islets of each metallocene when anchored onto the aminated silicon wafers.
- Trzebiatowska-Gusowska, Monika,Ga?gor, Anna,Coetsee, Elizabeth,Erasmus, Elizabeth,Swart, Hendrik C.,Swarts, Jannie C.
-
p. 393 - 403
(2013/10/01)
-
- Manipulating the diastereoselectivity of ortholithiation in planar chiral ferrocenes
-
The sense of asymmetric ortholithiation directed by a chiral oxazoline may be inverted simply by the choice of achiral ligand. Comparison of results with a number of ferrocenyl oxazoline derivatives suggests that lithiation takes place by coordination to the oxazoline nitrogen irrespective of the ligand used.
- Herbert, Simon A.,Castell, Dominic C.,Clayden, Jonathan,Arnott, Gareth E.
-
supporting information
p. 3334 - 3337
(2013/07/26)
-
- Synthesis and biological evaluation of ferrocene-containing bioorganometallics inspired by the antibiotic platensimycin lead structure
-
The recent discovery of the natural product platensimycin (1) as a new antibiotic lead structure has triggered the synthesis of numerous organic derivatives for structure-activity relationships (SAR) in order to improve the poor in vivo efficacy of 1. The synthesis, characterization, and biological evaluation of the first four ferrocene-containing bioorganometallic compounds based on the platensimycin lead structure are reported herein, namely 3-(4,4-diferrocenoylpentanamido)-2,4-dihydroxybenzoic acid (2), 3-(4,4-diferrocenoylbutanamido)-2,4-dihydroxybenzoic acid (3), 3-{4-(acetylferrocenoyl)butanamido}-2,4-dihydroxybenzoic acid (4), and 3-(4-ferrocenoylbutanamido)-2,4-dihydroxybenzoic acid (5). All new compounds were unambiguously characterized by all common analytical methods, including 1H and 13C NMR, mass spectrometry, IR spectroscopy, and elemental analysis. Furthermore, the single-crystal X-ray structures of methyl 4,4-diferrocenoylbutanoate (9), methyl 4,4-diferrocenoylpentanoate (10), 4,4-diferrocenoylpentanoic acid (14), 4,4-diferrocenoylbutanoic acid (15), and 4-(acetylferrocenoyl)butanoic acid (16) were also determined. Among 2-5 and their intermediate carboxylic acids tested, only 3 was found to inhibit selectively the growth of S. aureus Mu50 strain (VISA) at a minimum inhibitory concentration (MIC) value of 128 μg/mL.
- Patra, Malay,Gasser, Gilles,Wenzel, Michaela,Merz, Klaus,Bandow, Julia E.,Metzler-Nolte, Nils
-
p. 4312 - 4319
(2010/12/20)
-
- Specific features of oxidation of ferrocenylacetic acid with molecular oxygen in the absence and in the presence of Bronsted acids
-
Comparative analysis of the specific features of autooxidation of ferrocenylacetic acid (FcCH2COOH) in organic solvents at 30-50°C in the absence and in the presence of trifluoroacetic acid (processes 1 and 2 respectively) was carried out. It w
- Fomin,Shirokov
-
p. 2304 - 2316
(2010/04/29)
-
- Features of the oxidation of certain hydroxy derivatives of ferrocene with molecular oxygen in organic solvents
-
Features of the oxidation of hydroxymethylferrocene with molecular oxygen in organic solvent in the presence of weak and strong Broensted acids were studied. The resulting data were compared with published data on ferrocene and hydroxyferrocene oxidation, which made it possible to assess the trend in the oxidation mechanism in going from ferrocene π complexes to their hydroxyferrocene and hydroxymethylferrocene analogs. A conclusion was drawn that each of the ferrocenes reacts with oxygen in quite a specific way.
- Fomin,Shirokov,Polyakova
-
p. 1361 - 1370
(2009/02/07)
-
- Synthesis of ferrocenoate esters, amides and other ferrocenoyl derivatives using ferrocenoyl fluoride. A comparison of the reactions of ferrocenoyl fluoride in [bmim][BF4] with the microwave-promoted solvent-free reactions of ferrocenoyl fluoride
-
Simple, efficient and convenient routes for the synthesis of ferrocenoyl derivatives are described. They involve either the reaction of nucleophilic compounds and DMAP with ferrocenoyl fluoride in [bmim][BF4] or the solvent-free reactions of nucleophilic compounds with ferrocenoyl fluoride promoted by microwaves.
- Imrie, Christopher,Elago, Elago R.T.,Williams, Nadia,McCleland, Cedric W.,Engelbrecht, Pieter
-
p. 4959 - 4966
(2007/10/03)
-
- New synthesis of ferrocene monocarboxylic acid and systematic studies on the preparation of related key-intermediates
-
An improved technique for the preparation of ferrocenecarboxaldehyde and two new methods for the synthesis of ferrocenemonocarboxylic acid from the aldehyde or from acetyl ferrocene are described. Using the aldehyde or the monocarboxylic acid as starting materials, some important ferrocene key intermediates were prepared: monochlorocarbonyl ferrocene, alkali metal and ammonium ferrocenoates, ferrocene carboxyaldehyde diethylacetal, ferrocenecarboxamide, et..., as well as a new ferrocene derivative: piperazinium diferrocenoate.
- Neto, Alberto Federman,Miller, Joseph,De Andrade, Vania Faria,Fujimoto, Susana Yumi,De Freitas Afonso, Marcia Maisa,Archanjo, Fernando Costa,Darin, Vitor Andre,Andrade E Silva, Marcio Luis,Borges, Aurea Donizete Lanchote,Del Ponte, Gino
-
p. 209 - 216
(2008/10/08)
-
- Protonation and acylation of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2
-
The reactions of the heterometallic complexes (μ-H)Os3(μ-O2CC5H4FeCp)(CO)10 (1) and Fe{(μ-O2CC5H4)(μ-H)Os3(CO)10}2 (2) with CF3COOH, CF3SO3H, and AcCI were studied. The reaction of 1 with CF3COOH involves interaction with the Cp ligands, protonation of the O atom of the bridging carboxylate group, and oxidative degradation of the complex. At low concentrations, CF3SO3H protonates the O atom of the bridging carboxylate group, while at high concentrations, degradation of the complex takes place. The reaction of complex 2 with either CF3COOH or low concentrations of CF3SO3H results in successive elimination of two [(μ-H)Os3(CO)10] cluster fragments due to protonation of the O atoms of the carboxylate groups. In the case of high CF3SO3H concentrations, the Os-Os bonds of both cluster fragments of 2 are also protonated to give the [Fe{(μ-O2CC5H4)(μ-H)2Os3(CO)10}2]2+ dication. The Friedel-Crafts acylation of 1 takes place only when a large excess of AcCl and AlCl3 is used to give two new complexes, (μ-H)Os3(μ-O2CC5H4FeC5H4C(O)CH3)(CO)10 and (μ-H)Os3(μ-O2CC5H3C(O)CH3 FeCp)(CO)10 in a 2 : 1 ratio.
- Maksakov,Slovohotova,Golovin,Babailov
-
p. 2451 - 2458
(2007/10/03)
-
- An investigation of the chemistry of ferrocenoyl derivatives. The synthesis and reactions of ferrocenoyl imidazolide and its derivatives
-
Ferrocenoyl imidazolide is synthesized readily from ferrocenecarboxylic acid in one step. It is a red crystalline compound that is stable at 5°C in the dark and it acts as an efficient ferrocenoyl equivalent. It reacts rapidly with alkoxides to give esters and with thiolates to give thioesters. Its reaction with Lawesson's reagent gave diferrocenoyl disulfide. Attempts to make diferrocenoyl peroxide by reacting ferrocenoyl imidazolide with hydrogen peroxide were unsuccessful. Ferrocenoyl imidazolide is converted into triferrocenylmethanol and diferrocenyl ketone in one step by reacting it with ferrocenyl-lithium. The X-ray crystal structures of ferrocenoyl phenyl sulfide and diferrocenoyl disulfide are described.
- Imrie, Christopher,Cook, Leanne,Levendis, Demetrius C.
-
p. 266 - 275
(2007/10/03)
-
- Synthesis of unbridged bis(2-R-indenyl)zirconocenes containing functional groups and investigations in propylene polymerization
-
Five new indenyl zirconium metallocenes with 2-alkyl and 2-aryl substituents were synthesized and characterized. For the synthesis of the ligand the di-Grignard reagent 1,2-bis(magnesiomethyl)benzene dichloride was explored as a synthon to 2-substituted indenes. This procedure provides access to a variety of functionalized 2-indenylmetallocenes such as bis(2-ferrocenylindene)zirconium dichloride and bis(2-adamantylindenyl)zirconium dichloride. Crystallographic characterization of bis[2-(4-(dimethylamino)phenyl)indenyl] zirconium dichloride revealed an anti conformation with a coplanar orientation of the dimethylamino substituent to the aryl ring in the solid state. The polymerization behavior of all five zirconocene dichlorides in liquid propylene was studied in the presence of MAO at various temperatures, and the results were compared to those for the known catalyst system bis-(2-phenylindenyl)zirconium dichloride/MAO (M1/MAO). The productivity of the 2-arylindene metallocenes in propylene polymerization was on the order of 100-7000 kg of PP/((mol of Zr) h). In contrast, the (2-adamantylindenyl)metallocenes exhibited very low productivities of 6 kg PP/((mol of Zr) h) in propylene polymerization.
- Witte, Peter,Lal, Tapan K.,Waymouth, Robert M.
-
p. 4147 - 4155
(2008/10/08)
-
