Vanadyl acetylacetonate voacac 2 is used as a catalyst for epoxidation of allylic alcohols with the use of tertbutyl hydroperoxide as the reoxidant. Preparation and characterisation of metal acetylacetonate. Continuous wave and pulse epr spectroscopy is employed to determine the location of the voacac2 complexes in the mixedoxide. It is found that the magnitude of the vanadium nuclear hyperfine splitting constant decreases from 108. The reaction with a vanadyl reagent results in higher stereoselectivity as it bonds chelates to the oxygen 7 oh reagent oh o reagent. The structure of manganeseiii acetylacetonate is shown as below. Vanadyl acety lacetonate, voacac 2, is used as a precursor. Ac199590000, ac199590010, ac199590500, ac199592500 synonyms.
Hydroxycinnamic acids are rich in phenolic antioxidants and may reduce the incidence of degenerative diseases, such as cardiovascular disease and cancer, whose mechanism of action is believed to be initiated by free radicals. Ortolano, thomas russell, spectral studies on vanadyl complexes. Mononuclear anionic species vo 2 l, which were isolated as alkaline. Epoxidation of the caryophyllene allylic alcohols 3. Pdf controlling nuclearity and stereochemistry in vanadylv and.
Preparation of polymeric membranes with and without the catalyst. Vanadyl acetylacetonate is the chemical compound with the formula voacac 2, where acac is the conjugate base of acetylacetone. Since our earlier results clearly demonstrated that substituents at nitrogen of aminodiols exerted definite influence on the efficiency. Mechanistic insight into the cyclohexene epoxidation with voacac. The complex catalyzes epoxidation of allylic alcohols by peroxides. It is a bluegreen solid that dissolves in polar organic solvents. Vanadyl acetylacetonate 3153262 v69 spectrum chemical. The stereochemistry of vanadyl acetylacetonate catalyzed epoxidation of cyclic allylic alcohols with tcrfbutyl hy droperoxide is examined and.
Controlling nuclearity and stereochemistry in vanadylv. Vanadyl acetylacetonate, voacac 2, is the simplest. Material safety data sheet toxin and toxintarget database. Kinetics of oxidation of vanadyl acetylacetonate by oxygen in. The kinetics of oxidation of vanadyl acetylacetonate to voohomeacac by molecular o2 in meoh have been studied spectrophotometrically. Vanadiumcatalyzed epoxidation of cyclic allylic alcohols.
The bands in the range 4400029000 cm1 are attributed to the n. Use the link below to share a fulltext version of this article with your friends and colleagues. Stereoselective preparations of epoxy, fluoro and related. Located in yixing city a tourist city at the bank side of scenic taihu lake, wuxi zhanwang chemical reagent co. The reaction with a vanadyl reagent results in higher stereoselectivity as it bonds chelates to the oxygen 6 oh reagent oh o reagent. Vanadyl ir stretching writing a lab report for inorganic and i have to comment on how the different ligands affect the vo stretching in two different complexes.
Catalytic amounts of voacac2 coupled with tbutylhydroperoxide. Formation of trans epoxides by syn epoxidation is a consequence of the conformational flexibility of the ninemembered ring, which places. This complex features the vanadyl iv group, and many related compounds are known. Syntheses and spectral investigations 53 electronic spectra of the complexes were recorded in acetonitrile and in dmf, on a uvvis double beam uvd3500 spectrophotometer in the range 5000011100 cm1. Pdf thermal decomposition of vanadyl acetylacetonate.
Pdf synthesis, molecular structure and properties of oxo. It is generally immediately available in most volumes. Vanadyl acetylacetonate v69 3153262 c 10 h 14 o 5 v spectrum chemical important update all sales after march 2, 2020 are final and nonreturnable for covid19 related items. Vanadyl acetylacetonate is a blue complex with the formula voacac 2. A recent study used this compound to catalyze stereoselective synthesis of. Thermal decomposition of vanadyl acetylacetonate springerlink.
Chapter 5 118 program and recorded images were integrated and scaled using saintbruker. There is no warranty of accuracy or completeness of any information contained herein. Vanadyl acetoneacetate is not optically active, so there is no stereochemistry to consider. Beckman du manual spectrophometer with reflectance attach ment, using. Controlling nuclearity and stereochemistry in vanadylv and. Acros organics bvba janssen pharmaceuticalaan 3a 2440 geel. Esr studies and the electronic structure of vanadyl ion. Electron paramagnetic resonance study of intermolecular exchange coupling in an undiluted vanadyl complex. The reaction, which is pseudo firstorder with respect to voacac2 and o2, is inhibited by hacac and a vanadiumv complex. Epoxidation of 2 with tbuooh in the presence of vanadyl acetylacetonate voacac 2 as catalyst furnished epoxide 19 in a stereospecific reaction 35,42 44. Structural characterization and dft study of vivoacac2 in. Vanadyl acetylacetonate is the chemical compound with the formula voacac2, where acac. Preparation of vanadyl acetylacetonate voacac2py the. Structure in the electronic spectra of vanadyl acetylacetonate.
The tetracyanoethylenecatalyzed solvolysis shed some light on the stereochemistry of epoxidation. Stereochemistry of epoxidation of some caryophyllenols the. Epoxidations with tertbutyl hydroperoxidevanadyl acetylacetonate vanadyl acetylacetonate 19 mg, 0. However, acetylacetonate is a stronger ligand that displaces the water molecules.
Ketoenol equilibrium of acetylacetone and formation of acetylacetonate anion. Ultra high purity and high purity forms may be considered. Raman measurements were performed using a horibajobin yvon confocal labram raman microscope utilizing a 633 nm exci. Reaction of nh 4 vo 3 with the protoligands h 2 l gave the dinuclear complexes lovovol.
Feb 01, 2009 vanadyl acetoneacetate is not optically active, so there is no stereochemistry to consider. Epoxidation of methyl shode 7 gave 8 45 mg, 43% and 9 44 mg, 43%. New mechanism for the reduction of vanadyl acetylacetonate to. Stereoselective synthesis and investigation of isopulegol. The acac anion can act as a ligand towards metal ions, typically forming a bidentate complex where the metal is bound to the two oxygen atoms, thus forming a 6membered ring. Nov 22, 2018 controlling nuclearity and stereochemistry in vanadylv and mixed valent v iv v v complexes of oxido. The vanadiumcatalyzed epoxidation reaction voacac2tbutyl. The molecule is square pyramidal, with idealized c 2v symmetry. Stereochemistry of uranyl acetylacetonate hydrate 147 comyns et al. Stereochemistry of epoxidation of some caryophyllenols. Vanadyl acetylacetonate suppliers, manufacturers, cas no 3153.
Each calcination step was performed in a quartz rotary furnace under 50 mlmin. Yet, i havent been able to find anything about the characteristics of a typical vo ir spectrum. Stereochemistry of uranyl acetylacetonate monohydrate. Definition of vanadyl acetylacetonate in the dictionary. Pdf the complex voodaho oda ochcoo has been obtained by reaction of aqueous solutions of voacac with oxydiacetic acid. For working out the oxidation number of vanadium, oxygen counts as 2. Stereoselective reactions of alkenes massey university. Vanadyl acetylacetonate, or oxobis2, 4pentanedionovanadiumiv by the iupac naming system, is a deep blue crystal with several applications beyond the scope of this experiment. We report the structural characterization of vanadyl acetylacetonate in imidazolium room. The interest in the chemistry of oxovanadium complexes has. This complex features the vanadyliv group, and many related compounds are known.
Structural investigation of vanadylacetylacetonate. Synopsis derivatives of the tridentate 2,6pyridinedimethanol ligand were reacted with nh 4 vo 3 or voacac 2 acac acetylacetonate. The directing effect of the hydroxyl group within the substrate allows for highly diastereoselective epoxidation of olefins. The rate data were used to calculate the thermodynamic activation parameters. The electron spin resonance spectra of vanadyl acetylacetonate voacac 2 and a number of its adducts have been examined in benzene solution at ambient temperatures. The spectra have been analyzed and the components of the g tensor and of the vanadium hyperfine interaction tensors have been determined, and for the porphyrin the nitrogen extrahyperfine interaction tensor has been obtained. The vanadyl acetylacetonate was chosen as the v 2 o 5 precursor since it decomposes in air at relatively low temperature about 400 c with formation of vanadiumv oxide 20, 21. Voacac2 shows solvatochromism in the selected ionic liquids and behaves as in organic. Ir spectral analysis of oxovanadium acetylacetone biology essay. Acetylacetonate forms neutral complexes with most metals. Vox mixedoxide supported sba15 catalysts were prepared by the molecular designed dispersion method mdd using acetylacetonate complexes. Controlling nuclearity and stereochemistry in vanadylv and mixed valent v iv v v complexes of oxido. Esr studies of coordination to the sixth position of vanadyl. Abstract in this study, a new mechanism for the reduction of vanadyl acetylacetonate, voacac2, to vanadium acetylacetonate, vacac3.
Vanadyl acetylacetonate is one of numerous organometallic compounds also known as metalorganic, organoinorganic and metalloorganic compounds sold by american elements under the trade name ae organometallics for uses requiring nonaqueous solubility such as recent solar energy and water treatment applications. In the procedures right at the begining it says add 2. Vanadyliv complexes of ferulic and cinnamic acid with quinic acid 1,2. Two different synthesis route depositions are presented to prepare these mixedoxide catalysts in a very controlled way. Compounds 1, 3, 8, 9 and 10 were prepared via their benzoyl. It is used in organic chemistry as a catalyst for the epoxidation of allylic alcohols by. Information and translations of vanadyl acetylacetonate in the most comprehensive dictionary definitions resource on the web. Vanadyl acetylacetonate filled pvdf membranes as the core of. Our previous work has shown that epoxidation with tbuooh in the presence of vanadyl acetylacetonate voacac2 as a catalyst can be successfully applied to prepare a new family of neoisopulegolbased chiral aminodiol libraries 57. Partial oxidation of ethanol on vanadia catalysts on. Voacac 2, vanadiumivoxy acetylacetonate cas number 3153262. Vanadyl acetylacetonate is the chemical compound with the formula voc5h7o22. Insitu fourier transform infrared spectroscopy gas phase studies of vanadium iv oxide coating by atmospheric pressure chemical vapour deposition using vanadyl iv acetylacetonate, thin solid films, 2008, vol.
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