The ring opening and oligomerisation reactions of an epoxide and an episulfide on aluminosilicates in the liquid phase

• Authors: András Fási , István Pálinkó , Ágnes Gömöry , Imre Kiricsi
• Languages of publication: EN

Abstracts

EN

The ring opening reactions of propylene oxide (methyloxirane) or ethylene sulfide )thiirane) were studied in the liquid phase over HZSM-5, HY-FAU or AlMCM-41 at 363 K or 423 K and under 1 or 20 bar pressure in a batch reactor. The proportion of these routes were identified: (i) single C−O scission providing non-cyclic products, (ii) double C−O cleavage leading to the loss of the heteroatom, (iii) oligomerisation resulting in cyclic dimers and the trimer of thiirane and a non-cyclic dimer of methyloxirane. The reaction pathway depended on the conditions and the solid acids used. Findings are compared to those in the gas phase over the same solid acids. Transformation mechanisms are also suggested.

Keywords

EN

Propylene oxide (methyloxirane); ethylene sulfide (thiirane); HZSM-5; HY-FAU; AlMCM-41; liquid phase; transformation channels; comparison to the gas-phase reactions

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2005
• Volume: 3
• Issue: 2
• Pages: 230-244

Dates

published

1 - 6 - 2005

online

1 - 6 - 2005

Contributors

author

András Fási

• Department of Applied and Environmental Chemistry, University of Szeged, Rerrich B. tér 1, H-6720, Szeged, Hungary

author

István Pálinkó

• Department of Organic Chemistry, University of Szeged, Dóm tér 8, H-6720, Szeged, Hungary

author

Ágnes Gömöry

• Chemical Research Center, Hungarian Academy of Sciences, PO Box 19, H-1525, Budapest, Hungary

author

Imre Kiricsi

• Department of Applied and Environmental Chemistry, University of Szeged, Rerrich B. tér 1, H-6720, Szeged, Hungary

References

• [1] Some of the very recent references: J.-A. Ma and D. Cahard: “Towards perfect catalytic asymmetric synthesis: Dual activation of the electrophile and the nucleophile”, Angew. Chem. Int. Ed., Vol. 43, (2004), pp. 4566–4583; N. Kato, D. Tomita, K. Maki, M. Kanai and M. Shibasaki: “Practical synthesis of chiral ligands for catalytic enantioselective cyanosylilation of ketones and ketoimines”, J. Org. Chem., Vol. 69, (2004), pp. 6128–6130. http://dx.doi.org/10.1002/anie.200300635[Crossref]
• [2] M.G. Silvestri and C.-H. Wong: “Opening of thiiranes: Preparation of orthogonal protected 2-thioglyceraldehyde”, J. Org. Chem., Vol. 66, (2001), pp. 910–914; R.D. Adams, K.M. Brosius and O. Sung-Kwon: “The catalytic synthesis of thiacrowns from thiiranes by Group VI and VII transition metal carbonyl complexes”, J. Organomet. Chem., Vol. 652, (2002), pp. 51–59. http://dx.doi.org/10.1021/jo001392v[Crossref]
• [3] J.C. Zomerdijk and M.W. Hall: “Technology for the manufacture of ethylene oxide”, Catal. Rev. Sci. Eng., Vol. 23, (1981), pp. 163–185; R.A. van Santen and H.P.C.E. Kuipers: “The mechanism of ethylene epoxidation”, Adv. Catal., Vol. 35, (1987), pp. 265–321.
• [4] B. Tamami and K.P. Borujeny: “Synthesis of thiiranes from oxiranes using cross-linked polystyrene supported aluminium chloride as a catalyst”, Synth. Commun., Vol. 34, (2004), pp. 65–70. http://dx.doi.org/10.1081/SCC-120027239[Crossref]
• [5] Some very recent exemplary references: S. Gil, M. Torres, N. Ortúzar, R. Wincewicz and M. Parra: “Efficient addition of acid enediolates to epoxides”, Eur. J. Org. Chem., (2004), pp. 2160–2165; K. Suda, T. Kikkawa, S. Nakajima and T. Takanami: “Highly regio- and stereoselective rearrangement of epoxides to aldehydes catalyzed by high-valent metalloporphyrin complex, Cr(TPP)OTf”, J. Am. Chem. Soc., Vol. 126, (2004), pp. 9554–9555; A.K., Chakraborti, S. Rudrawar and A. Kondaskar: “Lithium bromide, an inexpensive and efficient catalyst for opening of epoxide rings by amines at room
• [6] R.-H. Fan and X.-L. Hou: “Efficient ring-opening reaction of epoxides and aziridines promoted by tributylphosphine in water”, J. Org. Chem., Vol. 68, (2003), pp. 726–730; V. Polshettiwar and M.P. Kaushik: “CsF-Celite catalyzed regio- and chemoselective SN 2 type ring opening of epoxides with thiol”, Catal. Commun. Vol. 5, (2004), pp. 515–518; H. Shargi, M.M. Eskandari and R. Ghavami: “A facile conversion of epoxides to halohydrins with elemental halogen using isonicotinic hydrazide (isoniazide) as a new catalyst”, J. Mol. Catal. A, Vol. 215, (2004), pp. 55–62. http://dx.doi.org/10.1021/jo025983s[Crossref]
• [7] G. Islas-Gonzales, C. Puigjaner, A. Vidal-Ferran, A. Moyano, A. Riera and M.A. Pericas: “Boron trifluoride-induced reactions of phenylglycidyl ethers: a convenient synthesis of enantiopure, stereodefined fluorohydrins”, Tetrahedron Lett., Vol. 45, (2004), pp. 6337–6341. http://dx.doi.org/10.1016/j.tetlet.2004.06.069[Crossref]
• [8] F. Badalassi, G. Klein, P. Crotti and J.-L. Reymond: “Fluorescence assay and screening of epoxide opening by nucleophiles”, Eur. J. Org. Chem., (2004), pp. 2557–2566; O. Equey, E. Vrancken and A. Alexakis: “Regioselective SN2 opening of vinylic epoxides with trialkylzincates and trialkylaluminates”, Eur. J. Org. Chem., (2004), pp. 2151–2159; D.M. Hodgson, C.D. Bray and N.D. Kindon: “Enamines from terminal epoxides and hindered lithium amides”, J. Am. Chem. Soc., Vol. 126, (2004), pp. 6870–6871.
• [9] Á. Molnár, I. Bucsi and M. Bartók: “Selective ring-opening of isomeric 2-methyl-3-phenyloxiranes on oxide catalysts”, Stud. Surf. Sci. Catal., Vol. 59, (1991), pp. 549–556; Á. Molnár, I. Bucsi, M. Bartók, G. Resofszki and G. Gáti: “Characterization of acid-base properties of oxides via the selective ring-opening of 2-methyloxirane”, J. Catal., Vol. 129, (1991), pp. 303–306.
• [10] T. Imanaka, Y. Okamato and S. Teranishi: “Isomerization of propylene oxide on zeolite catalysts”, Bull. Chem. Soc., Jpn., Vol. 45, (1972), pp. 3251–3254; S. Matsumoto, M. Nitta and K. Amoura: “Catalytic properties of synthetic A-type zeolite. III. Effect of ion exchange on the 1,2-epoxybutane-isomerization activity”, Bull. Chem. Soc., Jpn., Vol. 47, (1974), pp. 1537–1538; H. Takeuchi, K. Kitajima, Y. Yamamato and K. Mizuno: “The use of proton-exchanged X-type zeolite in catalyzing ring-opening reactions of 2-substituted epoxides with nucleophiles and its effect on regioselectivity”, J. Chem. Soc., Perkin Trans., Vol. 2, (1993), pp. 199–2023; M. Onaka, K. Sugita, H. Takeuchi and Y. Izumi: “Regioselective ring openings of 2,3-epoxy alcohols with ammonium halides and sodium benzenethiolate supported on zeolite CaY”, J. Chem. Soc., Chem. Commun., (1988), pp. 1173–1174; W. Hölderich and H. van Bekkum: “Zeolites in organic synthesis”, Stud. Surf. Sci. Catal., Vol. 58, (1991), pp. 631–727; A. Liebens, C. Mahaim and W.F. Hölderich: “Selective isomerization of α-pinene oxide with heterogeneous catalysts”, Stud. Surf. Sci. Catal., Vol. 108, (1997), pp. 587–594; R. Dimitrova, V. Minkov and N. Mincheva: “Zeolite catalyzed ring opening of styrene oxide”, Appl. Catal. A, Vol. 145, (1996), pp. 49–55; H. Ogawa, Y. Miyamoto, T. Fujigaki and T. Chihara: “Ring-opening of 1,2-epoxyalkane with alcohols over H-ZSM-5 in liquid phase”, Catal. Lett., Vol. 40, (1996), pp. 253–255; M.V.R. Reddy, S.V. Pitre, I. Bhattacharya and Y.D. Vankar: “General synthetic methods. 5. Zeolite (H-ZSM5) catalyzed regioselective isomerization of glycidic esters to α-hydroxy-β,γ-unsaturated esters”, Synlett, (1996), pp. 241–242; R.A. Sheldon, J.A. Elings, S.K. Lee, H.E.B. Lempers and R.S. Downing: “Zeolite-catalyzed rearrangements in organic synthesis”, J. Mol. Catal. A, Vol. 134, (1998), pp. 129–135; C. Meyer, W. Laufer and W.F. Hölderich: “Selective isomerization of isophorone epoxide over zeolites”, Catal. Lett., Vol. 53, (1998), pp. 131–134; A. Liebens, W. Laufer and W.F. Hölderich: “Ring opening reaction of 4,4,5,8-tetramethyl-1-oxaspiro-[2,5] octane to 2,2,3,6-tetramethyl-cyclohexane-carbaldehyde with heterogeneous catalysts”, Catal. Lett., Vol. 60, (1999), pp. 71–75. http://dx.doi.org/10.1246/bcsj.45.3251[Crossref]
• [11] A. Fási, I. Pálinkó and I. Kiricsi: “Ring-opening, dimerization and oligomerization reactions of methyloxirane on solid acid and base catalysts”, J. Mol. Catal. A, Vol. 208, (2004), pp. 307–311. http://dx.doi.org/10.1016/S1381-1169(03)00546-6[Crossref]
• [12] G.K.S. Prakash, T. Matthew, S. Krishnaraj, E. Marinez and G.A. Olah: “Nafion-H catalysed isomerization of epoxides to aldehydes and ketones”, Appl. Catal. A, Vol. 181, (1999), pp. 283–288. http://dx.doi.org/10.1016/S0926-860X(98)00400-1[Crossref]
• [13] P. Nanayakkara and H. Alper: “Palladium-catalyzed alkylation of vinyl oxirane with substituted allenes. Direct access to bifunctionalized allylic alcohols”, J. Org. Chem., Vol. 69, (2004), pp. 4686–4691; K. Nakano, M. Katayama, S. Ishihara, T. Hiyama and K. Nozaki: “An alternative route to protected alcohols: Cobalt-catalyzed hydroformylation of epoxides and in situ protection of β-hydroxyaldehydes by HC(OMe)3”, Synlett, (2004), pp. 1367–1370. http://dx.doi.org/10.1021/jo040139i[Crossref]
• [14] I. Pálinkó and J. Ocskó: “Hydrogen pressure dependence in the ring opening of methyloxirane over silica-supported Pd and Rh catalysts; Effect of high temperature on ring-opening routes”, J. Mol. Catal. A, Vol. 104, (1996), pp. 261–265; I. Pálinkó: “Activity and regioselectivity in the ring-opening reaction of methyloxirane at metal-metal oxide interfaces”, J. Mol. Catal., A, Vol. 140, (1999), pp. 195–198. http://dx.doi.org/10.1016/1381-1169(95)00191-3[Crossref]
• [15] A. Sadorge, P. Sauvageot, O. Blacque, M.M. Kubicki, C. Moise and J-C. Leblanc: “Desulfurization and ring opening of thiirane induced by tantalocene trihydride complexes: synthesis, reactivity and X-ray structure of Cp′2Ta(:S)(S-iPr) with Cp′ =η5-C5H4tBu”, J. Organomet. Chem., Vol. 575, (1999), pp. 278–285. http://dx.doi.org/10.1016/S0022-328X(98)01007-9[Crossref]
• [16] A. Kameyama, M. Kiyota and T. Nishikubo: “New ring-opening reaction of thiiranes with carboxylic acid derivatives catalyzed by quaternary onium salts”, Tetrahedron Lett., Vol. 35, (1994), pp. 4571–4574. http://dx.doi.org/10.1016/S0040-4039(00)60731-1[Crossref]
• [17] A. Fási, Á. Gömöry, I. Pálinkó and I. Kiricsi: “Cyclodimerisation and cyclotrimerisation during the ring-opening reactions of ethylene sulfide (thiirane) over acidic molecular sieves and alumina”, Catal. Lett., Vol. 76, (2001), pp. 95–98. http://dx.doi.org/10.1023/A:1016759605883[Crossref]
• [18] A. Fási, I. Pálinkó and I. Kiricsi: “Ring-opening and dimerization reactions of methyl- and dimethyloxiranes on HZSM-5 and CuZSM-5 zeolites”, J. Catal., Vol. 188, (1999), pp. 385–392. http://dx.doi.org/10.1006/jcat.1999.2669[Crossref]
• [19] A. Fási, Á. Gömöry, I. Pálinkó and I. Kiricsi: “Isomerization and dimerization reactions of methyloxirane over various types of zeolite”, J. Catal., Vol. 200, (2001), pp. 340–344. http://dx.doi.org/10.1006/jcat.2001.3186[Crossref]
• [20] H. Lechert and R. Kleinwort: “High-alumina ZSM-5”, In: H. Robson (Ed.): Verified Syntheses of Zeolitic Materials, 2nd revised Ed., Elsevier, 2001, p. 198.
• [21] J.M. Kim, J.H. Kwak, S. Jun and R. Ryoo: “Ion exchange and thermal stability of MCM-41”, J. Phys. Chem., Vol. 99, (1995), pp. 16742–16747. http://dx.doi.org/10.1021/j100045a039[Crossref]
• [22] J.S. Beck, J.C. Vartuli, G.J. Kennedy, C.T. Kresge, W.J. Roth and S.E. Schramm: “Molecular or supramolecular templating: defining the role of surfactant chemistry in the formation of microporous and mesoporous molecular sieves”, Chem. Mater., Vol. 6, (1994), pp. 1816–1821. http://dx.doi.org/10.1021/cm00046a040[Crossref]
• [23] R. Schmidt, D. Akporiaye, M. Stöcker and O.H. Ellestad: “Synthesis of a mesoporous MCM-41 material with high levels of tetrahedral aluminum”, J. Chem. Soc., Chem. Commun., (1994), pp. 1493–1494.
• [24] K.M. Reddy and C. Song: “Synthesis of mesoporous molecular sieves: influence of aluminum source on Al incorporation in MCM-41”, Catal. Lett., Vol. 36, (1995), pp. 103–109. http://dx.doi.org/10.1007/BF00807213[Crossref]
• [25] X. Zhao, C.Q. Lu and J. Millar: “Advances in mesoporous molecular sieve MCM-41”, Ind. Eng. Chem. Res. Vol. 35, (1996), pp. 2075–2090. http://dx.doi.org/10.1021/ie950702a[Crossref]
• [26] A.B. Smith III, S.M. Pitram, A.M. Boldi, M.J. Gaunt, C. Sfouggatakis and W.H. Moser: “Multicomponent Linchpin couplings. Reaction of dithiane anions with terminal epoxides, epichlorohydrin, and vinyl epoxides: Efficient, rapid, and stereocontrolled assembly of advanced fragments for complex molecule synthesis”, J. Am. Chem. Soc., Vol. 125, (2003), pp. 14435–14445. http://dx.doi.org/10.1021/ja0376238[Crossref]
• [27] J.M. McMurry: Organic Chemistry, 5th Ed., Brooks/Cole, 2000, p. 720.
• [28] I. Hannus, Z. Kónya, P. Lentz, J.B. Nagy and I. Kiricsi: “Multinuclear MAS NMR investigation of zeolites reacted with chlorofluorocarbons”, J. Mol. Struct., Vol. 482–483, (1999), pp. 359–364. http://dx.doi.org/10.1016/S0022-2860(98)00766-2[Crossref]
• [29] A. Fási, I. Pálinkó, Á. Gömöry and I. Kiricsi: “Ring opening reactions of methyloxirane over DZSM-5 and DAlMCM-41 zeolites-A mechanistic study”, Stud. Surf. Sci. Catal., Vol. 135, (2001), p. 233; CD-ROM edition 23P15. http://dx.doi.org/10.1016/S0167-2991(01)81480-4[Crossref]

Identifiers

DOI

10.2478/BF02475993