With manganic acetate

A wide variety of substituted y-butyrolactones can be prepared directly from olefins and aliphatic carboxylic acids by treatment with manganic acetate. This procedure is illustrated in the preparation of 7-( -OCTYL)-y-BUTYROLACTONE. Methods for the synthesis of chiral molecules are presently the target of intensive investigation. One such general method developed recently is the employment of certain chiral solvents as auxiliary agents in asymmetric synthesis. The preparation of (S.SM+H, 4-BIS(DIMETHYLAMINO)-2,3-DIMETHOXY-BUTANE FROM TARTARIC ACID DIETHYL ESTER provides a detailed procedure for the production of this useful chiral media an example of its utility in the synthesis of (+)-(/ )-l-PHENYL-l-PEN-TANOL from benzaldehyde and butyllithium is provided. 

Most of the reported work on the kinetics of catalysed polycondensation by transesterification is quite recent and in the main deals with the preparation of PET, though related work on other esters from ethylene glycol has been reported. Reinisch et al. [34] found that the melt polycondensation leading to poly(ethylene sebacate) in 3—4 mm films under vacuum, with manganous acetate as catalyst, was second order from p = 0.70 to p = 0.97. Rate coefficients are listed in Table 5 for this reaction, for the formation of poly(ethylene sebacate-co-terephthalate) and for PET. 

The oxidation of thebaine with manganic acetate first gives [xvi], which on hydrolysis with 20 per cent, hydrochloric acid affords after three minutes at 100° C. the dihydroxyketone [xvrr], and 14-hydroxy-codeinone [xvm] after twenty minutes [98]. The 14-substituted codeinones are discussed in Chapter XVIII. 

Hydroxycodeinono has also been prepared by the oxidation of thebaine with sodium diohromate in aqueous acetic acid or sulphuric aoid [3-5, 10-11], Tho oxidation of thobaino with manganic acetate gives 8- (or J4-) aootyl- 8 14-diliydroxydihydrothobaino [vi], which can... 

An interesting example is the oxidation of dimethylaniline (39). Oxidation of (39) with manganic acetate in acetic acid gives as the sole isolable product 4,4 -bis(dimethylamino)diphenylethane (40). Apparently the first step in the reaction is dealkylation by the mechanism of equation (7.69),... 

The present research was focused on the study of acetaldehyde oxidation rising air with aqueous mangan acetate catalyst in mechanically stirred tank reactor. 

Manganous acetate (4H2O) [6156-78-1 ] M 245.1. Crystd from water acidified with acetic acid. 

Commercially available Mn(OAc)3 2H20 has been used for most oxidative cyclizations. This reagent can also be prepared easily from potassium permanganate and manganous acetate in acetic acid [1], Anhydrous Mn(OAc)3 is slightly more reactive than the dihydrate. Reaction times with the anhydrous reagent are usually somewhat shorter but the yields of products are usually comparable. Both tri-fluoroacetic acid and potassium or sodium acetate have been used with Mn(OAc)3. 

Manganic acetate (manganese triacetate), Mn(OCOCH3)3, is prepared by refluxing a solution of manganese acetate tetrahydrate in acetic acid with potassium permanganate [S03]. This oxidant hydroxylates ben-zylic methylene groups [416] and forms lactones from terminal alkenes [803, 804] (see equation 88). 

Dihydrofumnes. Dihydrofuranes are obtained in fair to high yield by reaction of readily enolizable ketones (/3-diketones, /3-keto esters) with olefins in the presence of 2 eq. of manganic acetate. The reaction is considered to involve generation and oxidation of free radicals. 

Diketones. The reaction of enol esters with ketones at 50-70° in the presence of manganic acetate (2 eq.) leads to 1,4-diketones in moderate yields ... 

---