Rendiconti Lincei

, Volume 24, Issue 3, pp 239–249 | Cite as

Pyrolytic behavior of simple chiral molecules: secondary aromatic alcohols

Chirality in Chemistry and Biophysics
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Abstract

The present study relates to the problem of the thermal stability of simple chiral molecules. Rough estimates of the temperatures under which the chirality phenomenon could survive have been reported. The chiral molecules tested in the present study were 1-phenylethanol (PE) enantiomers [(S(−)- and R-(+)-], S-(−)-1-phenylpropanol [PPe] and S-(+)-trifluoro-1-phenylethanol. The pyrolysis of the above-mentioned chiral alcohols with and without catalysts at different temperatures (200–600 °C) has been carried out. In the presence of catalysts the partial racemization (≤20 %) and formation of products like styrene, acetophenone, benzaldehyde and chiral benzylic ethers have been detected in the case of PE. Without catalysts almost no racemization was observed and product formation was not appreciable. The kinetics of racemization has been calculated and a tentative mechanism has been proposed. A principal components analysis model was created using the results obtained with all catalysts at different temperatures and with the main products, i.e., acetophenone, dibenzylic ethers and styrene to discriminate the catalysts on the basis of their effects.

Keywords

Chiral 1-phenylethanol enantiomers Pyrolysis-GC/MS Racemization Enantiomeric excess Catalysts 
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Notes

Acknowledgments

The author thanks Camilla Montesano for experimental part realization.

References

  1. Bada JL, McDonald GD (1995) Amino acid racemization on Mars: implications for the preservation of biomolecules from an extinct martian biota. Icarus 114:139–143CrossRefGoogle Scholar
  2. Basiuk VA, Navarro-Gonzalez R, Basiuk EV (1998) Pyrolytic behavior of amino acids and nucleic acid bases: implications for their survival during extraterrestrial delivery. Orig Life Evol Biosphere 28:167–193CrossRefGoogle Scholar
  3. Blank JG, Miller GH, Ahrens MJ, Winans RE (2001) Experimental shock chemistry of aqueous amino acid solutions and the cometary delivery of prebiotic compounds. Orig Life Evol Biosphere 31:15–51CrossRefGoogle Scholar
  4. Boyer B, Keramane E, Roque JP, Pavia AA (2000) BiBr3, an efficient catalyst for the benzylation of alcohols: 2-phenyl-2-propyl, a new benzyl-type protecting group. Tetrahedron Lett 41:2891–2894CrossRefGoogle Scholar
  5. Brereton RG (2003) Chemometrics data analysis for the laboratory and chemical plant, Wiley, New YorkGoogle Scholar
  6. Brucato JR, Mennella V, Colangeli L, Rotundi A, Palumbo P (2002) Production and processing of silicates in laboratory and in space. Planet Space Sci 50:829–837CrossRefGoogle Scholar
  7. Cohen BA, Chyba CF (2000) Racemization of meteoritic amino acids. Icarus 145:272–281CrossRefGoogle Scholar
  8. Costa LFA, Lemos F, Ramoa Ribeiro F, Cabral JMS (2008) Zeolite screening for the racemization of 1-phenylethanol. Catal Today 133:625–631CrossRefGoogle Scholar
  9. de los Arcos T, Garnier MG, Seo JW, Oelhafen P, Thommen V, Mathys D (2004) Influence of iron–silicon interaction on the growth of carbon nanotubes produced by chemical vapor deposition. J Phys Chem B 108:7728–7734CrossRefGoogle Scholar
  10. Ebbers EJ, Ariaans GJA, Houbiers JPM, Bruggink A, Zwanenburg B (1997) Controlled racemization of optically active organic compounds: prospects for asymmetric transformation. Tetrahedron 53:9417–9476CrossRefGoogle Scholar
  11. Gomez R, Lopez T, Tzompantzi F, Garciafigueroa E, Acosta DW, Novaro O (1997) Zirconia/silica sol–gel catalysts-effect of the surface heterogeneity on the selectivity of 2-propanol decomposition. Langmuir 13:970–973CrossRefGoogle Scholar
  12. Keheyan Y, Montesano C (2010) The influence of mineral catalysts on racemization of secondary alcohols under pyrolytic temperatures. J Anal Appl Pyrolysis 89:286–293CrossRefGoogle Scholar
  13. Keheyan Y, Montesano C (2011) The influence of mineral catalysts on racemization of secondary alcohols under pyrolytic temperatures. II part. J Anal Appl Pyrolysis 92:324–331CrossRefGoogle Scholar
  14. Ledoux MJ, Pham-Huu C (2001) Silicon carbide: a novel catalyst support for heterogeneous catalysis. CATTECH 5:226–246CrossRefGoogle Scholar
  15. Molster F, Kemper C (2005) Crystalline silicates. Space Sci Rev 119:3–28CrossRefGoogle Scholar
  16. Parvelescu AN, Jacobs PA, de Vos DE (2009) Support influences in the Pd-catalyzed racemization and dynamic kinetic resolution of chiral benzylic amines. Appl Catal A Gen 368:9–16CrossRefGoogle Scholar
  17. Pasadakis N, Yiokari C, Varotsis N, Vayenas C (2001) Characterization of hydrotreating catalysts using the principal components analysis. Appl Catal A 207:333–341CrossRefGoogle Scholar
  18. Pattiya A, Titiloye JO, Bridgwater AV (2010) Evaluation of catalytic pyrolysis of cassava rhizome by principal component analysis. Fuel 89:244–253CrossRefGoogle Scholar
  19. Peterson E, Horz F, Chang S (1997) Modification of amino acids at shock pressures of 3.5 to 32 GPa. Geochim Cosmochim Acta 61:3937–3950CrossRefGoogle Scholar
  20. Wagnière GH (2007) On chirality and the universal asymmetry Wiley–VCH, ZurichGoogle Scholar
  21. Wilson NC, Muscat J, Mkhonto D, Ngoepe PE, Harrison NM (2005) Structure and properties of ilmenite from first principles. Phys Rev B 71:075202/1–075202/9CrossRefGoogle Scholar
  22. Wuyts S, de Vos DE, Veerport F, Depla D, de Gryse R, Jacobs PA (2003) A heterogenous Ru-hydroxyapatite catalyst for mild racemization of alcohols. J Catal 219:417–424CrossRefGoogle Scholar
  23. Wuyts S, de Temmerman K, Jacobs PA, de Vos DE (2005) Acid zeolites as alcohol racemization catalysts: screening and application in biphasic dynamic kinetic resolution. Chem Eur J 11:386–397CrossRefGoogle Scholar
  24. Wuyts S, Wahlen J, Jacobs PA, de Vos DE (2007) Heterogeneous vanadium catalysts for racemization and chemoenzymatic dynamic kinetic resolution of benzylic alcohol. Green Chem 9:1104–1108CrossRefGoogle Scholar
  25. Xu B-Q, Yamaguchi T, Tanabe K (1988) Acid-base bifunctional behavior of ZrC2 in dual adsorption of CO2 and NH3. Chem Lett 166:1663–1666CrossRefGoogle Scholar

Copyright information

© Accademia Nazionale dei Lincei 2013

Authors and Affiliations

  1. 1.ISMN-CNR, c/o Department of ChemistryUniversity “La Sapienza”RomeItaly

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