Synthesis of methotrexate and ferrocene conjugates as potential anticancer agents david dago nda a thesis submitted to the faculty of science, university of the witwatersrand, in fulfilment of the requirements for the degree of doctor of philosophy of science. Recent advances in the synthesis of ferrocenebased heterocycles by multicomponent reactions. The bonding mode of in the ferrocene based organometallic compound metal ion complexes. Synthesis, structures and electrochemical studies james a. Synthesis and characterization of ferrocene derivatives. Metallosupramolecular architectures formed with ferrocenelinked bisbidentate ligands.
The first known synthesis may have been made in the late 1940s by unknown. Applications of ferrocene and its derivatives homogeneous catalysis olefin polymerization hydroformylation organic synthesis chiral catalysis materials science conducting materials fuel additives bioconjugates conjugates of fc with amino acids, proteins, dna, rna, new medicine candidates ferrocene tamoxifen ferroquine bio. Ferrocenecontaining polyacetylenes are synthesized in good yields by cucatalyzed click reactions of azido moieties of poly6chloro1phenyl1hexyneco6azido1phenyl1hexyne and poly14azidohexyloxyphenyl2phenylacetylene with ethynylferrocene. Because of the instability of the cyclopentadiene monomer, it must be used immediately after cracking. Physical and chemical analyses including ir, 1hnmr, and melting point support and confirm the successful synthesis of approximately 10. Macroscale and microscale organic experiments, 4th. Synthesis of soluble ferrocenebased polythiophenes and. Synthesis of ferrocene based organometallic compounds. C5h52, is of historical importance since its discovery and structural characterisation in the early 1950s sparked extensive research into the chemistry of metal sandwich compounds. This mixture was stirred under cold bath and a thf solution 10 ml containing nmm 0. Solvent is removed by distillation, and the ferrocene is extracted from the residue with several portions of. Cracking of dicyclopentadiene and the synthesis of ferrocene reference. The article processing charge apc for publication in this open access journal is 1800 chf swiss francs, a 50% discount will apply to papers accepted for publication in the special issue ferrocene and ferrocenecontaining compounds. This experiment shows the friedelcrafts acylation reaction to obtain acetylateferrocene.
The crude ferrocene prepared in this synthesis is a dull yellow. For this purpose, the key element to design ferrocenebased dyes is the conjugated pyran unit that links two ferrocene moieties to each other. Charge a 25ml round bottom flask with ferrocene 1g and acetic anhydride 3. What links here related changes upload file special pages permanent link. Synthesis of polymers containing crown ether and ferrocene.
Exposures were for 5 days per week for 2 weeks, with 2 or 3 additional days of exposure to fulfill experimental protocol. All the organometallic polymers are completely soluble in common organic solvents such as. Recently, we developed a method for the synthesis of racemic 1alkyl3,3dimethyl3,4dihydroferrocenocpyridines 6 via the ritter reaction of 2methyl1ferrocenylpropane1ol with the corresponding nitriles in the presence of methanesulfonic acid. Nanosecond uv laser pulses are used to compare the evolution of the particle size distribution as a function of laser irradiation time. Synthesis of ferrocene tethered heteroaromatic compounds using. Other applications of ferrocene b using ferrocene for analytic methods in total synthesis burn, n. At the same time, there have been no reports describing the synthesis of ferroceneindolizines. If d 5d symmetry is assumed,so that there is a centre of symmetry in the ferrocene molecule through the fe atom there will be centro. Synthesis and characterisation of ferrocenyl chalcone. Pdf solidstate mechanochemical synthesis of ferrocene. To synthesize the aromatic organotransition metal compound ferrocene. Record the ir and the uvvis in ethanol spectra of ferrocene, 1 h nmr in cdcl. Synthesis of coumarin or ferrocene labeled nucleosides via.
Students are required to consult the given references for the necessary procedures. Pdf synthesis of ferrocene based organometallic compounds. A final yield was unable to be determined due to the mass of water from humidity in the air not being negligible since the. Tfcp 5,10,15,20 tetraferrocenylporphyrin2 have also been prepared and. Recent advances in the synthesis of ferrocenebased. Synthesis of polymers containing c r o w n ether and ferrocene units umit tunca department of chemistry, istanbul technical university, maslak 80626, istanbul, turkey received 27 no vember 1995 polyketone containing crown ether and ferrocene moieties was obtained by means of the reaction of 1,1ferrocenedicarboxylicacid with dibenzo18crown. Synthesis of ferrocene annulated trifluoromethylated. In this particular experiment, studies have been done for the synthesis and the reactivity of ferrocene. In the gas phase, the two cyclopentadienyl rings are eclipsed, but the solid exists in several phases in which the rings are coparallel but in. Submitted papers should be well formatted and use good english. Purpose and background of the experiment the principal aims of this experiment are.
Synthesis and reactions of ferrocene the archetypal organometallic compound ferrocene, fe. In the fume hood, slowly transfer a 5 cm tall column of silica gel using a clean pipet. An introduction to the synthesis and reactions of ferrocene. Fisherjohns melting point apparatus midac ftir spectrometer, ftnmr introduction.
The easiest way to carry out the sublimation is with two small same. The structure of the organometallic compound ferrocene, fec5h52, is shown on the right. Organometallic sandwich compounds were first synthesized in 1951. The medicinal chemistry of ferrocene and its derivatives.
Following the name of ferrocene, came the term metallocene, a major departure of classical model of ligand coordination. The shifting of these groups at lower frequency in the range 162045 cm1 in the metal complexes, when these values compared to ferrocene based organometallic compound. Ferrocene is an organometallic compound with the formula fec 5h 5 2. Synthesis and biological evaluation of ferrocenecontaining bioorganometallics inspired by the antibiotic platensimycin lead structure. The synthesis and characterization of a series of ferrocene based ionic compounds is discussed in this study. Synthesis and photophysical studies of porphyrinferrocene. Synthesis of ferrocenecontaining polyacetylenes by click. This document is a short summary of a detailed student lab guide which. This book captures the multidisciplinary nature of ferrocene research, including topics such as ferrocenecontaining polymers, ferrocenecontaining thermotropic liquid crystals, chiral ferrocene derivatives, and ferrocenecontaining chargetransfer materials.
A band at 1690 cm1 in ferrocene based organometallic compound is due to c n vibration. The reactions were carried out in a similar manner as presented in scheme 1. Metallosupramolecular architectures formed with ferrocene linked bisbidentate ligands. Preparation and purification of ferrocene abstract ferrocene was synthesized using the reagents ferrous chloride tetrahydrate and cracked cyclopentadiene. Catalyzing interest in organometallic chemistry joe derosa 12116 part iii. Metallosupramolecular architectures formed with ferrocene. Pure ferrocene can be obtained by sublimation at atmospheric pressure. The reaction was successful but produced a very low yield of only 0. Pdf solidstate mechanochemical reactions of ironii chloride with cyclopentadienides of alkaline metals or thallium, which lead to the.
Crowley a adepartment of chemistry, university of otago, po box 56, dunedin. The crystallographic information files for both the compounds are provided in the esi. All the bond angles and bond lengths are in the same ranges as those. Male and female f344rats and b6c3f1mice were exposed in whole body exposure chambers to filtered air or 2. Ferrocenebased polythiophenes are the promising class of the functional materials, but mostly the polythiophenes are insoluble in common solvents except some derivatives of polythiophenes like poly3hexylthiophene p3ht. With applications ranging from asymmetric catalysis to magnetic materials, ferrocene is one of the most versatile building blocks in synthesis. Synthesis and photophysical studies of porphyrinferrocene conjugates article pdf available in journal of porphyrins and phthalocyanines 1110. Ferrocenes wiley online books wiley online library. The carbonmetal bond of the ferrocene structure was a new concept of pbonding of a carbocyclic ring to a metal atom.
The volume of aqueous nh 42ceno 36 added to the solution was negligible 2. Synthesis of ferrocene carboxylic acid 4,6dimethoxy1,3,5triazin2yl ester 2e ferrocene carboxylic acid 1 0. The crude ferrocene then underwent sublimation resulting in 0. Research laboratory of mcrs, department of chemistry, zanjan branch, islamic azad university, zanjan p.
Introduction the discovery of ferrocene was a landmark achievement in the field of organometallics that sparked the search for other. Investigating the synthesis and reactivity of ferrocene. Herein, two new ferrocenebased thiophene monomers, 2thiophen3yl ethyl ferrocenoate and 2thiophen3yl methyl. Synthesis of bare iron nanoparticles from ferrocene hexane. We used intermolecular staudinger ligation for the preparation of fluorescent and electrochemically labeled nucleosides. Synthesis and electronic properties of ferrocenefilled. Ferrocene is a cyclopentadienyl iron ii complex with the formula. In the present study, in continuance of our previous study on the synthesis of ferrocene containing materials, the aim is to incorporate the known properties of ferrocene into 2, 6dimethyl4hpyran4ylidene fragment. Ferrocene was the first organometallic sandwich compound to be made and the structure was not determined until a year after it was first produced. To compare purification by recrystallization and sublimation. As the label we used either coumarin4acetic acids 1ac or ferrocene derivative 16 figure figure1, 1, which were synthesised in our department as part of studies into new ligands.
Ferrocene1 massachusetts institute of technology department of chemistry 5. These compounds contain bisferrocene sulfonates as the anion, with 1alkyl3methylimidazolium species as cations, where the alkyl groups are. The primary orbital interactions that form the metal. Ferrocene vapors were produced by heating ferrocene aerosols. Three new indiumiii polyferrocenyl porphyrins xintfcp complexes x cl, oh, or fc. Silica gel is such a fine powder that it can be transferred using a pipet just like a liquid. Ferrocene abstract in this experiment, ferrocene was synthesized chemically with ferrous chloride and cyclopentadiene. Figure 2 a gives an hrtem image for an empty doublewalled carbon nanotube dwnt with an outer diameter of 4. Overlay of 1h nmr spectra of reactants and reaction mixtures during the synthesis of ferrocene.