Atmosphere peracetic acid

Oxidation of Bis (1-methyl-2-acetoxypropyl) selenide in the Presence of 2-Butene. The oxidation of the selenide was conducted at 5°C. in glacial acetic acid solution saturated with 2-butene. The initial reaction was discontinued after adding 0.3 mole of peracetic acid per mole of selenide. The temperature was raised to 45°C., and the reaction was allowed to proceed for 15 minutes under a 2-butene atmosphere. These steps were repeated several times until the addition of 7 moles of peracetic acid per mole of selenide was completed. 

Conventionally peracetic acid is produced in a tank reactor in the presence of homogeneous acid catalyst. In the process, sulfuric acid catalyst is first charged into the reactor, after which acetic acid and hydrogen peroxide are fed into the reactor. The mixture is heated up and equilibrium reaction (1) takes place. When homogeneous acid catalyst is used, separation of it from equilibrium mixture is carried out in a distillation column. When equilibrium is reached, sub-atmospheric pressure is drawn in the reactor. Vaporization of the reaction mixture begins. In the distillation column acetic acid, hydrogen peroxide and peracetic acid are separated from sulphuric acid catalyst (Swem, D., 1970). The simplified scheme of the conventional process is illustrated in Figure 3. 

The off-gases, which entrain small amounts of products and reactants, are scrubbed with water and crude acetic add, and then discharged to the atmosphere. The recovered condensates are recycled. The liquid stream drawn off from the reactor is first rid of most of the peracetic acid it contains by heating in an inert atmosphere around 85 to 90 C, followed by distillation. 

The a-olefln was epoxidized with peracetic acid in benzene in the presence of sulfuric acid as a catalyst. A pure 1,2-epoxyalkane was obtained by repeated vacuum distillation. The monoethanolamine (9 moles) was reacted with 1,2 epoxyalkane (1 mole) dropwise for 1.5 hours. After removal of excess monoethanolamine under reduced pressure, the residue of reaction product was subjected to vacuum distillation in an atmosphere of nitrogen to give HEA in 70-80% yields based upon 1,2-epoxyalkane. 

SDMA in toluene for 20 min at 0° under an argon atmosphere gave the 5-C-(phenylphosphinyl) compound 124, which, on acid hydrolysis, afforded the 5-C-(phosphinyl)hexopyranose 125. This was treated with acetic anhydride-pyridine, to give the peracetates (126), from which crystalline l,2,4-tri-0-acetyl-3,6-di-0-benzyl-5-deoxy-5-C-[(S)-phenyl-phosphinyl]-/ -D-glucopyranose-4C1 (127) was isolated in 2% overall yield from 123 none of the other diastereoisomers of 127 were obtained. Structure 127 was established by 400-MHz, -n.m.r. spectroscopy (see Section 11,5). 

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