Unique Salt Effect on the High Yield Synthesis of Acid-Labile Terpene Oxides Using Hydrogen Peroxide under Acidic Aqueous Conditions

Abstract

Acid-labile epoxides such as α-pinene oxide are (effectively) synthesized in high yield from the epoxidation of terpenes with aqueous H₂O₂ catalyzed by Na₂WO₄, [Me(n-C₈H₁₇)₃N]HSO₄, and PhP(O)(OH)₂ in the presence of Na₂SO₄ as an auxiliary additive under organic solvent-free conditions at ambient temperature. Origin of the salt effect is considered that the addition of a saturated amount of Na₂SO₄ to aqueous H₂O₂ strongly inhibited the undesired hydrolysis of the acid-labile epoxide products, despite the highly acidic reaction conditions.

oxidation - catalysis - epoxides - terpenoids - green chemistry

References

1a Ullmann’s Encyclopedia of Industrial Chemistry   5th ed., Vol. A9:  Gerhartz W. Yamamoto YS. Kaudy L. Rounsaville JF. Schulz G. Wiley-VCH; Weinheim: 1987.  p.531 

1b Kirk-Othmer Encyclopedia of Chemical Technology   4th ed., Vol. 9:  Kroschwitz JI. Howe-Grant M. Wiley; New York: 1994.  p.377 

1c Kirk-Othmer Encyclopedia of Chemical Technology   4th ed., Vol. 9:  Kroschwitz JI. Howe-Grant M. Wiley; New York: 1994.  p.730 

2 Larock RC. In Comprehensive Organic Transformations   2nd ed.:  Wiley; New York: 1999.  p.915 

3a Strukul G. In Catalytic Oxidations with Hydrogen Peroxide as Oxidant   Kluwer Academic Publishers; Dordrecht: 1992. 

3b Jones CW. In Applications of Hydrogen Peroxide and Derivatives   RSC; Cambridge: 1999. 

4a Trost BM. Science  1991,  254:  1471 

4b Sheldon RA. Chem. Ind.  1992,  903 

For recent reviews, see:

5a Applied Homogeneous Catalysis with Organometallic Compounds   2nd ed.:  Cornils B. Herrmann WA. Wiley-VCH; Weinheim: 2002. 

5b Lane BS. Burgess K. Chem. Rev.  2003,  103:  2457 

5c Grigoropoulou G. Clark JH. Elings JA. Green Chem.  2003,  5:  1 

5d Modern Oxidation Methods   Bäckvall J.-E. Wiley-VCH; Weinheim: 2004. 

5e Mizuno N. Yamaguchi K. Kamata K. Coord. Chem. Rev.  2005,  249:  1944 

6a Payne GB. Williams PH. J. Org. Chem.  1959,  24:  54 

6b Venturello C. Alneri E. Ricci M. J. Org. Chem.  1983,  48:  3831 

6c Ishii Y. Yamawaki K. Ura T. Yamada H. Yoshida T. Ogawa M. J. Org. Chem.  1988,  53:  3587 

7a Sato K. Aoki M. Ogawa M. Hashimoto T. Noyori R. J. Org. Chem.  1996,  61:  8310 

7b Sato K. Aoki M. Ogawa M. Hashimoto T. Panyella D. Noyori R. Bull. Chem. Soc. Jpn.  1997,  70:  905 

7c Noyori R. Aoki M. Sato K. Chem. Commun.  2003,  1977 

8a Sienel G. Rieth R. In Ullmann’s Encyclopedia of Industrial Chemistry   6th ed., Vol. 12:  Wiley-VCH; Weinheim: 2003.  p.279 

8b Eggersdorfer M. In Ullmann’s Encyclopedia of Industrial Chemistry   6th ed., Vol. 35:  Wiley-VCH; Weinheim: 2003.  p.653 

8c Swift KAD. Top. Catal.  2004,  27:  143 

8d Corma A. Iborra S. Velty A. Chem. Rev.  2007,  107:  2411 

8e Bicas JL. Dionísio AP. Pastore GM. Chem. Rev.  2009,  109:  4518 

9a Kon Y. Ono Y. Matsumoto T. Sato K. Synlett  2009,  1095 

9b Kon Y. Hachiya H. Ono Y. Matsumoto T. Sato K. Synthesis  2011,  1092 

10a Hou S.-Y. Zhou Z.-H. Lin T.-R. Wan H.-L. Eur. J. Inorg. Chem.  2006,  1670 

10b Maheswari PU. Tang X. Hage R. Gamez P. Reedijk J. J. Mol. Catal. A: Chem.  2006,  258:  295 

11 Kolehmainen E. Laihia K. Heinänen M. Rissanen K. Fröhlich R. Korvola J. Mänttäri P. Kauppinen R.
J. Chem. Soc., Perkin Trans. 2  1993,  641 

12a Kopperman HL. Hallcher RCSr. Riehl A. Carlson RM. Caple R. Tetrahedron  1976,  32:  1621 

12b Liu W. Rosazza JPN. Synth. Commun.  1996,  26:  2731 

13 Grigoropoulou G. Clark JH. Tetrahedron Lett.  2006,  47:  4461 

14a McDevit WF. Long FA. J. Am. Chem. Soc.  1952,  74:  1773 

14b Long FA. McDevit WF. Chem. Rev.  1952,  51:  119 

15 Hofmeister F. Arch. Exp. Pathol. Pharmacol.  1887,  24:  247 

16a Poulson SR. Harrington RR. Drever JI. Talanta  1999,  48:  633 

16b Görgényi M. Dewulf J. Langenhove HV. Héberger K. Chemosphere  2006,  65:  802