Communication pubs.acs.org/jchemeduc
Permaleic Acid: Baeyer−Villiger Oxidation of Cyclododecanone Douglass F. Taber* and Jack Qiu Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States S Supporting Information *
ABSTRACT: A simple procedure for the preparation of 12-dodecanolide from cyclododecanone is available.
KEYWORDS: Second-Year Undergraduate, Organic Chemistry, Laboratory Instruction, Hands-On Learning/Manipulatives, IR Spectroscopy, Oxidation/Reduction, Mechanisms of Reactions, Synthesis, Thin Layer Chromatography 5, for example, demonstrates the importance of hydrogen bonding in promoting the oxidation. In practice, the CH2Cl2 solution of 5 can be prepared ahead of time by the instructor. This preparation has been carried out without difficulty on a scale sufficient to supply 50 students. It has been reported5 that the liquid 12-dodecanolide 3 is readily polymerized to a white solid with a molecular weight in excess of 10,000 by warming it with commercial lipase. This could be an interesting additional exercise for the student.
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n undergraduate laboratory experiment centered on formation of the oxime from cyclododecanone 1 and subsequent Beckmann rearrangement to the lactam 2 (eq 1) was recently described.1 The Baeyer−Villiger oxidation2 of 1 to 3 could complement this laboratory exercise, but 1 is a sluggish participant in that reaction.3
HAZARDS
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ASSOCIATED CONTENT
Chemicals required are methylene chloride, 30% aqueous hydrogen peroxide, acetic anhydride, maleic anhydride, cyclododecanone, potassium hydroxide, and sodium sulfite. When dealing with any of the solvents or reagents in this laboratory exercise, standard safety precautions apply. Wear protective gloves and proper protective clothing, as permaleic acid is known to cause skin irritation. It would be convenient to keep a liquid alkene in the lab (e.g., cyclooctene) to immediately rub on any accidentally exposed skin. Avoid direct ingestion or inhalation of any solvents or reagents.
Fortunately, permaleic acid 5 (eq 2) has been developed as a particularly effective reagent for Baeyer−Villiger oxidation. 4
Using reagent 5, 1 is transformed into 3 overnight at room temperature. Alternatively, the reaction can be stored for a week at room temperature without ill effect. The lactone 3 is an oil, which makes it easy to record its IR spectrum. The transformation can also be monitored by thinlayer chromatography. The Baeyer−Villiger workup can be done while at the same time carrying out the conversion of 1 to 2, if so desired. The 13C and 1H NMR data for 3 have been published.3b As the Baeyer−Villiger procedure requires no unusual laboratory equipment or reaction conditions, the synthesis of 12-dodecanolide 3 from cyclododecanone 1 will be a simple yet instructional procedure for any undergraduate to perform. In addition to laboratory techniques, the students will have the opportunity to further research several current and important topics in organic chemistry. The efficacy of reagent © XXXX American Chemical Society and Division of Chemical Education, Inc.
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S Supporting Information *
Student instructions, instructor notes, CAS registry numbers. This material is available via the Internet at http://pubs.acs.org.
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
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dx.doi.org/10.1021/ed400083m | J. Chem. Educ. XXXX, XXX, XXX−XXX
Journal of Chemical Education
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Communication
REFERENCES
(1) Taber, D. F.; Straney, P. J. The Synthesis of Laurolactam from Cyclododecanone via a Beckmann Rearrangement. J. Chem. Educ. 2010, 87, 1392. (2) Permaleic acid has not previously been mentioned in this Journal. For other undergraduate laboratory procedures for Baeyer−Villiger oxidation, see: (a) Kjonaas, R. A.; Clemons, A. E. The Baeyer−Villiger Oxidation with Trifluoroacetic Acid and Household Sodium Percarbonate. J. Chem. Educ. 2008, 85, 827−828. (b) Esteb, J. J.; Hohman, J. N.; Schlamadinger, D. E.; Wilson, A. M. A Solvent-Free Baeyer−Villiger Lactonization for the Undergraduate Organic Laboratory: Synthesis of γ-t-Butyl-ε-caprolactone. J. Chem. Educ. 2005, 82, 1837−1838. (c) Slawson, C.; Stewart, J.; Potter, R. Biocatalytic Lactone Generation in Genetically Engineered Escherichia coli and Identification of Products by Gas Chromatography-Mass Spectroscopy. J. Chem. Educ. 2001, 78, 1533−1534. (d) Anoune, N.; Hannachi, H.; Lantéri, P.; Longeray, R.; Arnaud, C. Use of Theoretical Chemistry To Explain Baeyer−Villiger Oxidations of Methoxy Aromatic Aldehydes. J. Chem. Educ. 1998, 75, 1290−1290. (e) Stephan, E. Baeyer−Villiger Oxidation of Indan-1-ones: Monitoring of the Reaction by VPC and IR Spectroscopy. J. Chem. Educ. 1995, 72, 1142−1143. (3) (a) For the Baeyer−Villiger oxidation of cyclododecanone with H2O2, see: Kamae, K.; Obora, Y.; Ishii, Y. Baeyer−Villiger oxidation of cycloalkanones with in situ generated hydrogen peroxide from alcohols and molecular oxygen using NHPI as a key catalyst. Bull. Chem. Soc. Jpn. 2009, 82, 891−895. (b) For the Baeyer−Villiger oxidation of cyclododecanone with MCPBA (ten days), see: van der Mee, L.; Helmich, F.; de Bruijn, R.; Vekemans, J. A. J. M.; Palmans, A. R. A.; Meijer, E. W. Investigation of Lipase-Catalyzed Ring-Opening Polymerizations of Lactones with Various Ring Sizes: Kinetic Evaluation. Macromolecules 2006, 39, 5021−5027. (4) Bidd, I.; Kelly, D. J.; Ottley, P. M.; Paynter, O. I.; Simmonds, D. J.; Whiting, M. C. Convenient syntheses of bifunctional C12-acyclic compounds from cyclododecanone. J. Chem. Soc., Perkin Trans. 1 1983, 1369−1372. (5) Uyama, H.; Takeya, K.; Hoshi, N.; Kobayashi, S. LipaseCatalyzed Ring-Opening Polymerization of 12-Dodecanolide. Macromolecules 1995, 28, 7046−7050.
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dx.doi.org/10.1021/ed400083m | J. Chem. Educ. XXXX, XXX, XXX−XXX
