Cumyl Hydroperoxide1

[80-15-9]  · C9H12O2  · Cumyl Hydroperoxide  · (MW 152.19)

(oxidant useful for metal-catalyzed enantioselective epoxidation of allylic alcohols2 and enantioselective oxidation of sulfides to sulfoxides3)

Alternate Name: cumene hydroperoxide.

Physical Data: mp 44-45 °C; bp 100-101 °C/8 mmHg; d 1.030 g cm-3; flash point 56 °C.

Solubility: sol most organic solvents; slightly sol H2O (15 g L-1).

Form Supplied in: a colorless to light yellow solution consisting of 80% cumene hydroperoxide in cumene; widely available.

Analysis of Reagent Purity: iodometric titration.4,5

Handling, Storage, and Precautions: cumyl hydroperoxide (CHP) is an unusually stable hydroperoxide which is resistant but still susceptible to induced explosive decomposition.6 Like most alkyl hydroperoxides, CHP should be stored cold (ca. 0 °C) in the absence of light in a container, such as a polyethylene bottle, that is unlikely to shatter if there is pressure build up. Exposing pure or concentrated solutions of CHP to heat, acid, reducing materials, and transition metal salts should be avoided. Upon completion of reactions involving CHP, steps should be taken to destroy any remaining reagent safely. This can usually be done by exposing the reaction mixture to a mild reducing agent such as aqueous sodium sulfite, methyl sulfide, or triphenylphosphine.

Enantioselective Epoxidation of Allylic Alcohols.

While t-Butyl Hydroperoxide (TBHP) is most often used in the Sharpless-Katsuki asymmetric epoxidation of allylic alcohols to give scalemic epoxy alcohols, CHP is sometimes used to advantage.4 For example, CHP is reported to epoxidize allyl alcohol and methallyl alcohol enantioselectively, with yields higher than TBHP (eq 1). Epoxidation with CHP is also apparently faster than with TBHP. In general, CHP can substitute for TBHP without loss of enantioselectivity.

Enantioselective Oxidation of Sulfides to Sulfoxides.

CHP3 has been shown to be superior to TBHP7 as the oxidant for the enantioselective oxidation of prostereogenic sulfides to scalemic sulfoxides using Titanium Tetraisopropoxide, diethyl tartrate, and water (eq 2).8

Related Reagents.

t-Butyl Hydroperoxide; Triphenylmethyl Hydroperoxide.

1. (a) Patai, S. The Chemistry of Hydroxy, Ether and Peroxide Groups; Wiley: New York, 1993. (b) Patai, S. The Chemistry of Peroxides; Wiley: New York, 1983. (c) Swern, D. Organic Peroxides; Wiley: New York, 1970; Vol. 1. (d) Swern, D. Organic Peroxides; Wiley: New York, 1970; Vol. 2. (e) Swern, D. Organic Peroxides; Wiley: New York, 1972; Vol. 3. (f) Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed.; Wiley: New York, 1982; Vol. 17, pp 27-90. (g) Davies, A. G. Organic Peroxides; Butterworths: London, 1961. (h) Hawkins, E. G. E. Organic Peroxides; Spon: London, 1961. (i) Tobolsky, A. V.; Mesrobian, R. B. Organic Peroxides; Interscience: New York, 1954.
2. Woodward, S. S.; Finn, M. G.; Sharpless, K. B. JACS 1991, 113, 106.
3. Zhao, S. H.; Samuel, O.; Kagan, H. B. T 1987, 43, 5135.
4. (a) Mair, R. D.; Graupner, A. J. Anal. Chem. 1964, 36, 194. (b) Banerjee, D. K.; Budke, C. C. Anal. Chem. 1964, 36, 2367.
5. Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. JACS 1987, 109, 5765.
6. The explosion of a cumyl hydroperoxide manufacturing facility was recently reported. See Chem. Eng. News 1993, 71 (22), 4; 1993, 71 (42), 4.
7. (a) Pitchen, P.; Duñach, E.; Deshmukh, M. N.; Kagan, H. B. JACS 1984, 106, 8188. (b) Duñach, E.; Kagan, H. B. NJC 1985, 9, 1. (c) Kagan, H. B.; Duñach, E.; Nemecek, C.; Pitchen, P.; Samuel, O.; Zhao, S. H. PAC 1985, 57, 1911.
8. Zhao, S. H.; Samuel, O.; Kagan, H. B. OS 1990, 68, 49.

Bryant E. Rossiter&dead;

Brigham Young University, Provo, UT, USA

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