A simple and efficient synthesis of 3-substituted derivatives of pentane-2,4-dione
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Bartosz Staniszewski
and
Włodzimierz Urbaniak
Abstract
A novel and efficient method of synthesis of 3-substituted derivatives of pentane-2,4-dione is proposed, wherein cheaper and easily accessible chloro derivatives are conversed into more reactive iodo derivatives. The method is based on the Finkelstein reaction for which the literature suggests highly polar organic solvents as ideal reaction media. In the presented work, the use of industrially used ketones, especially methyl isobutyl ketone, is proposed. The use of MIBK as a solvent additionally allows an azeotropic removal of water from the reaction mixture, enabling the application of moisture sensitive alkylating agents i.e. (3-chloropropyl)trimethoxysilane. The obtained products are isolated through distillation, which does however not allow the separation of C-alkylation products from O-alkylation ones. The products not containing water-sensitive substituents were isolated as copper complexes. The pure product of C-alkylation was obtained by decomposition of the copper complex with a hydrochloric acid solution and extraction of the formed ligand to an organic phase i.e. hexane. The obtained ligand can be further purified by distillation.
[1] Aho, P., Backstrom, R., Koponen, A., Linden, I., Lotta, T., Lonnberg, K., Pippuri, A., & Pohto, P. (2003). European Patent No. 1,091,933. Munich: European Patent Office. Search in Google Scholar
[2] Burtoloso, A. C. B. (2005). Copper(II) acetylacetonate: An inexpensive multifunctional catalyst. Synlett, 2005, 2859–2860. DOI: 10.1055/s-2005-918920. Search in Google Scholar
[3] Charles, R. G. (1963). Tetraacetylethane. Organic Syntheses, 4, 869–871. Search in Google Scholar
[4] Davis, R. B., & Hurd, P. (1955). The reaction of some diketones with sodium acetylide. Journal of the American Chemical Society, 77, 3284–3287. DOI: 10.1021/ja01617a038. http://dx.doi.org/10.1021/ja01617a03910.1021/ja01617a038Search in Google Scholar
[5] Furuta, P., Deng, L., Garon, S., Thompson, M., & Frechet, J. (2004). Platinum-functionalized random copolymers for use in solution-processible, efficient, near-white organic lightemitting diodes. Journal of the American Chemical Society, 126, 15388–15389. DOI: 10.1021/ja0446247. http://dx.doi.org/10.1021/ja044624710.1021/ja0446247Search in Google Scholar
[6] Hirao, T., Sakaguchi, M., Ishikawa, T., & Ikeda, I. (1995). Oxovanadium-induced or-catalyzed oxidative allylation of 1,3-dicarbonyl compounds with allylsilanes. Synthetic Communications, 25, 2579–2585. DOI: 10.1080/00397919508011803. http://dx.doi.org/10.1080/0039791950801180310.1080/00397919508011803Search in Google Scholar
[7] Linden, G., & Farona, M. (1977). Polymer-anchored vanadyl catalysts for the oxidation of cyclohexene. Journal of Catalysis, 48, 282–291 document DOI: 10.1016/0021-9517(77)90101-4. http://dx.doi.org/10.1016/0021-9517(77)90101-410.1016/0021-9517(77)90101-4Search in Google Scholar
[8] Marquet, J., & Moreno-Mañas, M. (1979). Reactions of bis [pentane-2,4-dionato]cobalt(II) with alkyl halides. Synthesis, 1979, 348–350. DOI: 10.1055/s-1979-28675 http://dx.doi.org/10.1055/s-1979-28675Search in Google Scholar
[9] Martin, D. F., Fernelius, W. C., & Shamma, M. (1959). Bis-(β-diketones). III. Synthesis and properties of compounds of the type (RCO)(R′CO)CH-Y-CH(COR)(COR′). Journal of the American Chemical Society, 81, 130–133. DOI: 10.1021/ja01510a029. http://dx.doi.org/10.1021/ja01510a02910.1021/ja01510a029Search in Google Scholar
[10] Odunola, O. A., & Woods, J. A. O. (2001). Synthesis, electronic, and magnetic properties of some 3-substituted 2,4-pentanedionatooxovanadium(IV) complexes and their 4-methylpyridine adducts. Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 31, 1297–1310. DOI: 10.1081/SIM-100106865. http://dx.doi.org/10.1081/SIM-10010686510.1081/SIM-100106865Search in Google Scholar
[11] Pande, A. (2005). Nickel acetyl acetonate [Ni(acac)2]. Synlett, 2005, 1042–1043. DOI: 10.1055/s-2005-864829. http://dx.doi.org/10.1055/s-2005-86482910.1055/s-2005-864829Search in Google Scholar
[12] Pohto, P., Aho, P. A., Backstrom, R. J., Honkanen, E. J., Linden, I., & Nissinen, E. (1994). European Patent No. 0357,403. Munich: European Patent Office. Search in Google Scholar
[13] Shepherd, T. (1970). 3-Alkyl pentane-2,4-diones - a convenient synthetic method. Chemistry & Industry, 1970, 561. Search in Google Scholar
[14] Tembe, G., Ganseshpure, P., & Satish, S. (1998). Manganese(II) β-diketonate catalyzed oxidation of cyclohexane by tertbutyl hydroperoxide. Reaction Kinetics and Catalysis Letters, 63, 385–389. DOI: S0133-1736(97)89612-7. http://dx.doi.org/10.1007/BF0247541610.1007/BF02475416Search in Google Scholar
[15] Uffner, M., Jefferson, D., Coe, C., & Beitchman, B. (1979). U.S. Patent No. 4,138,385. Washington D. C.: U.S. Patent and Trademark Office. Search in Google Scholar
[16] Urbaniak, W. (2005). Polish Patent No. 188,732. Warsaw: Patent Office of the Republic of Poland. Search in Google Scholar
[17] Urbaniak, W., & Schubert, U. (1991). An efficient synthesis of R3Si(CH2)n-substituted acetylacetone derivatives. Liebigs Annalen der Chemie, 1991, 1221–1223 DOI: 10.1002/jlac.1991199101209. http://dx.doi.org/10.1002/jlac.199119910120910.1002/jlac.1991199101209Search in Google Scholar
[18] Urbaniak, W., & Schubert, U. (1994). Polish Patent No. 165,181. Warsaw: Patent Office of the Republic of Poland. Search in Google Scholar
[19] Wehner, W., Friedrich, H., Malzacher, K., Mehner, H., & Drewes, R. (2001). U.S. Patent No. 6,194,494. Washington D. C.: U.S. Patent and Trademark Office. Search in Google Scholar
[20] Wilkins, J., & Wittbecker, E. (1953). U.S. Patent No. 2,659,711. Washington D. C.: U.S. Patent and Trademark Office. Search in Google Scholar
[21] Yokotani, H., Miyamoto, M., & Murata, T. (1973). U.S. Patent No. 3,708,540. Washington D. C.: U.S. Patent and Trademark Office. Search in Google Scholar
[22] Zhang, J., Luo, S., & Gui, L. (1997). Poly(methyl methacrylate)-titania hybrid materials by sol-gel processing. Journal of Materials Science, 32, 1469–1472. DOI: 10.1023/A:10185539014058. http://dx.doi.org/10.1023/A:1018553901058Search in Google Scholar
© 2008 Institute of Chemistry, Slovak Academy of Sciences
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Articles in the same Issue
- Biosynthesis of methanol from methane by Methylosinus trichosporium OB3b
- Influence of reaction medium composition on enzymatic synthesis of galactooligosaccharides and lactulose from lactose concentrates prepared from whey permeate
- Immobilization of modified penicillin G acylase on Sepabeads carriers
- Granulation of activated sludge in a laboratory upflow sludge blanket reactor
- Investigation of the effect of fluid elasticity on a cake filtration process
- Lab-scale testing of a low-loaded activated sludge process with membrane filtration
- Calcium sulphate scaling in membrane distillation process
- Characterization and filtration performance of coating-modified polymeric membranes used in membrane bioreactors
- Informational analysis of the grinding process of granular material using a multi-ribbon blender
- Effects of vessel baffling on the drawdown of floating solids
- N2O catalytic decomposition — effect of pelleting pressure on activity of Co-Mn-Al mixed oxide catalysts
- Intelligent control of a pH process
- Influence of suspended solid particles on gas-liquid mass transfer coefficient in a system stirred by double impellers
- A three-phase nonequilibrium model for catalytic distillation
- Membrane processes used for separation of effluents from wire productions
- A simple and efficient synthesis of 3-substituted derivatives of pentane-2,4-dione
- Formation of hydrated titanium dioxide from seeded titanyl sulphate solution
- Pyrolytic and catalytic conversion of rape oil into aromatic and aliphatic fractions in a fixed bed reactor on Al2O3 and Al2O3/B2O3 catalysts
- Oxidation of thiophene over copper-manganese mixed oxides
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