MMPP, monoperoxyphthalic acid

MMPP, monoperoxyphthalic acid magnesium salt MOMCl, chloromethyl methyl ether... 

The reaction of alkenes with peroxy acids provides for convenient and selective oxidation of double bonds. The peroxy acids most commonly used in the laboratory are m-chloroperoxybenzoic acid (mCPBA), monoperoxyphthalic acid magnesium salt (MMPP), peroxybenzoic acid, peroxyformic acid, peroxyacetic acid, trifluoroper-oxyacetic acid, and 7-butyl hydroperoxide f(CH3)3COOH]. The order of reactivity for... 

Pyrazolo[l,2-r-][l,3,4]oxadiazine derivative 188 is converted to the corresponding (V-oxide 189 by oxidation with magnesium monoperoxyphthalate (MMPP) or -chloroperbenzoic acid (MCPBA) (Equation 23) <2004CEJ737>. 

In the original patent published by Merck in 1995, rofecoxib (2) was synthesized in three steps from the known 4-(methylthio)acetophenone (10), prepared from the Friedel-Crafts acylation of thioanisole. As depicted in Scheme 2, oxidation of sulfide 10 using an excess of magnesium monoperoxyphthalate hexahydrate (MMPP, an inexpensive, safe and commercially available surrogate for w-CPBA) gave rise to sulfone 11, which was subsequently brominated with bromine and AICI3 to afford 2-bromo-l-(4-(methylsulfonyl)phenyl)ethanone (12). After recrystallization from 1 1 EtOAc/hexane, the pure phenylacyl bromide 12 was then cyclo-condensed with phenylacetic acid under the influence of l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to deliver rofecoxib (2) in... 

The synthesis of rofecoxib can be achieved by several different routes (Drugs Fut., 1998). A highly efficient synthesis for rofecoxib was recently described (Therien et al., 2001). As illustrated in Scheme 79, acetophenon (i) is prepared according to the literature, by Friedel-Crafts acylation with thioanisole. Oxidation with MMPP (magnesium monoperoxyphthalate hexahydrate) affords the sulfone (ii), which is reacted with bromine in chloroform in the presence of a trace amount of AICI3, to give (iii). Bromoketone (iii) is than coupled and cyclized in a second step, one-pot procedure with phenylacetic acid. Firstly, the mixture of bromoacetophenone (iii) and phenylacetic acid in acetonitrile is treated with... 

Another one-step addition reaction to C=C double bonds that forms three-membered rings is the epoxidation of alkenes with percarboxylic acids (Figure 3.19). Most often, meta-chloroperbenzoic acid (MCPBA) is used for epoxidations. Magnesium monoperoxyphthalate (MMPP) has become an alternative. Imidopercarboxylic acids are used to epoxidize olefins as well. Their use (for this purpose) is mandatory when the substrate contains a ketonic C=0 double bond in addition to the C=C double bond. In compounds of this type, percarboxylic acids preferentially cause a Baeyer-Villiger oxidation of the ketone (see Section 14.4.2), whereas imidopercarboxylic acids selectively effect epoxidations (for an example see Figure 14.35). 

A third one-step addition reaction to C=C double bonds that forms three-membered rings is the epoxidation of olefins with percarboxylic acids (Figure 3.14). Suitable percarboxylic acids must, however, not be (too) explosive. Thus, aromatic percarboxylic adds are preferable. Until recently one epoxidized almost exclusively with mefa-chloroper-benzoic acid (MCPBA). An alternative has become magnesium monoperoxyphthalate (MMPP). In the transition state of this type of epoxidation, four electron pairs are shifted simultaneously (which is a record in this book except for the Corey-Winter elimination in Figure 4.42). 

Chemoselective oxidation of sulfenimines 2 is a useful method for the preparation of sulfinimines 3.10-12 The oxidation was usually carried out with m-CPBA (3-chlo-roperbenzoic acid) in a biphasic mixture of chloroform and aqueous sodium bicarbonate and a variety of sulfinimines have been prepared in this way. Sulfinimines 3 were usually obtained as a single -isomer despite the fact that their precursors 2 may exist as mixtures of E- and Z-isomers.10 Other oxidants which have been demonstrated to be effective for oxidation include MMPP (magnesium monoperoxyphthalate)13 and chlorine.14,15... 

Isothiazolium salts react by S-oxidation and C-3 oxyfunctionalization with H202 (30%)/acetic acid or magnesium monoperoxyphthalate (MMPP) to stable mono-and bicyclic 3-hydroperoxysultims, -sultams, 3-hydroxysultams and 3-oxosultams, retaining the heterocyclic ring system. 

For these reasons, many products were developed in the past but were never commercialized. In the late 1980s, diperoxydodecanedioic acid (DPDDA) was test marketed as a laundry bleach. Magnesium monoperoxyphthalate (MMPP) was also tested in the 1990s as a bleach in detergent formulations. Today, the only peracid that has been commercialized on a limited scale is 8-phthalimidoperoxycaproic acid or PAP (trade name Eureco). 

Give the expected major product of reaction of magnesium monoperoxyphthalate (MMPP) with each alkene. In each case, also give the structure of the material formed upon hydrolysis in aqneons acid of the initial product. 

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