Epoxidation of Alkenes Mechanistic Determination

Epoxidation of alkenes using peroxyacids is one of the most fundamental reactions in organic chemistry, yet there are very few examples of laboratory experiments that illustrate this important reaction. The inherent instability of many epoxides in acidic solutions makes the synthesis of acid-sensitive epoxides by this route difficult. Frequently, the carboxylic acid formed from the peracid during epoxidation reacts with acid-sensitive epoxides to give hydroxyesters as the major product. Procedures have been developed for epoxidation of alkenes in the presence of buffers to minimize this problem.

Overview of the Experiment

This is a discovery-oriented lab experiment that illustrates epoxidation of alkenes as well as the reactivity of epoxides toward acids. The experiment involves reaction of p-methoxy-trans--methylstyrene (trans-anethole) 1 with m-chloroperoxybenzoic acid (MCPBA), in both the absence and presence of a buffer. Products obtained are of sufficient purity to allow analysis by spectroscopy without further purification. Based on the spectroscopic data and the proposed schemes, the mechanisms for the buffered and non-buffered reaction pathways will be determined. The identities of the products are conveniently determined by 1H NMR, 13C NMR, and IR spectroscopy. Each team consisting of two students carries out the epoxidation of trans-anethole, in both the absence and presence of a buffer. The entire reaction, including the work up, takes only about an hour. With the use of sufficient sample, both 1H NMR and 13C NMR spectra can be easily obtained in 15 minutes. Analysis of 1H NMR, 13C NMR, and IR spectra of the product obtained in both the presence and the absence of a buffer indicates the identity of the major product.

Proposed Mechanisms to consider

Questions to answer in determining the major products for each reaction pathway. 1. Are there peaks for epoxide hydrogens in the 1H NMR spectrum of the product obtained in the presence of buffer? Absence of buffer? 13 2. How many benzene ring carbons can be seen in the C NMR spectrum of the product obtained in the presence of buffer? Absence of buffer? 13 3. Are there any other carbons in the C spectra? If so, what functional group is indicated in each? 4. What functional groups are indicated by the IR spectra? 5. What is the theoretical yield of the product, assuming it is the epoxide? How does this compare to the observed yields? Outline your experimental procedure based on these excerpts from the journal article describing the synthesis

Notes

Other helpful Comments (1) Commercial MCPBA, available from ACROS chemicals, is 70 % per acid by weight. We confirmed this by iodometric titration according to the procedure of Vogel (Textbook of Practical Organic Chemistry, 5th Ed.; Vogel, A. I.; Longman Scientific and Technical: New York,1989, p 455) (2) Because trans-anethole is very inexpensive, it was chosen rather than the much more expensive p-methoxystyrene. (3) Peroxy acids (pKa ~ 8) are much weaker acids than carboxylic acids (pKa ~ 4). This allows for selective extraction of 3chlorobenzoic acid. However, some of the MCPBA does react with Na2CO3, as is evident by the fact that the reaction does not go to completion when only 1 equiv. of MCPBA is used in presence of Na2CO3. (4) The reaction mixture must be stirred very efficiently with a magnetic stir bar. (5) If the organic layer is not extracted several times with Na2CO3, some of the 3-chlorobenzoic acid still remains in the organic layer. (6) An alternative to the experiment described can be further purification of the ester by column chromatography (Rf 0.38, 40 % ethyl acetate-60 % hexanes). The epoxide is not stable to silica gel. (7) The ester and epoxide are not very volatile. Hence solvent can be easily removed using a water bath maintained at 50 C. The epoxide is very reactive and undergoes decomposition at higher temperatures.
Reference: Vol. 78 No. 1 January 2001 Journal of Chemical Education