Peracetic from oxidation

Instead of the peracetic acid oxidation just described, performic acid (prepared from 98 % formic acid and 90% hydrogen peroxide) may also be used as an oxidizing agent for the preparation of nitroso compounds. With this reagent, pentafluoronitrosobenzene and 4-nitrosotetrafluorobromobenzene have been prepared from the respective amines [85]. 

Peracetic acid oxidation of 2-carbamoylquinoxaline (94) at 20°-25° gives the monoxides 95 and 96, and at higher temperatures the 1,4-dioxide (97) is isolated in 50% yield, together with a small amount of the 1,4-dioxide of 2-amino-3-quinoxalinone.m However, Hayashi and co-workers report the isolation of only 96 from 94 using monoperphthalic acid in ether <10°.109 In their attempt to correlate the nature of 2-substitution with the formation of 1- versus 4-oxides, they examined the behavior of some 2-alkyl substituted quinoxalines 113,114 2-ethylquin-oxaline gives the 1- and 4-oxides and the 1,4-dioxide, 2-isopropylquin-oxaline yields the 4-oxide and the 1,4-dioxide however, 2-f-butylquin-oxaline only furnishes the 4-oxide because of steric hindrance.114 The N-oxidation of 2-phenyl- and 2-alkyl-3-phenyl-quinoxalines with monoperphthalic acid furnishes the products shown in Table 1.114... 

This category includes several heterocyclic iodanes coming mainly from benziodazoles or benziodoxoles or a combination of both. Among them, 1-hydroxy-l,2-benziodazole and its derivatives are of considerable interest. It is noted that the first iodane of this type, prepared in 1965 by peracetic acid oxidation of o-iodobenzamide, is not N- (as originally proposed) but O-acetyl (Scheme 26) [77]. 

Suitable control experiments had been carried out to establish that dibutyltin dichloride is not lost from the residue at 50 °C. and 12 mm. and to establish that the procedure for mercaptide removal (peracetic acid oxidation) did not interfere with the accuracy of the chloride analysis. 

Similar stereochemical possibilities are present when 11 is obtained from trans-l,3-dimethyl-3-hexene, 13, as a cross diperoxide from the ozon-olysis of 12 or from the peracetic acid oxidation of methyl ethyl ketone. 

The oxidative modification of peptides is a most interesting topic, but there is no suitable method available. The mthenium-catalyzed oxidation with peracetic acid provides a useful method for modification. For example, the reaction of N,C-pro-tected peptides containing glycine residues with peracetic acid in the presence of RUCI3 catalyst gives a-ketoamides 69 derived from oxidation at the Cf position of the glycine residue selectively (81%, conv. 70%) (Eq. 3.81) [139]. 

The configuration of the ether oxygen at C-1 in methyl angolensate (130) has been unambiguously shown to be a by a partial synthesis from 7-deacetyl-7-oxokhivorin via the deoxy-compound (131). The latter was converted by peracetic acid oxidation to the e-lactone (132) and this was opened by toluene-p-sulphonic acid in benzene to give the diene-lactone (133). Mild alkaline hydrolysis of the... 

Acid-catalysed peracetic acid oxidation of allobetulone (118) affords (119) and (120) in addition to the expected a-lactone. These results are relevant to the current interest in methods for removal of one or both C-4 methyls from triterpenoids... 

Thermolysis of the methylenecyclobutanone (237) in refluxing 1,2-dichlorobenzene gave a 82 18 mixture of the isomers (238) and (239), with (239) probably being formed from (238). Ozonolysis and peracetic acid oxidation of each of the isomers gave... 

The first synthesis of f-caprolactone was reported by Carothers(1). He also investigated its polymerization under the influence of heat cmd catalysts. Since then the polymerizations of this as well as that of other lactones were studied by many researchers. Throughout the 1950 s to the 1970 s the polymer formation and its properties were the subject of several investigations in our laboratories(2-5). Union Carbide is presently the commercial producer of the monomer and of a series of polymers which range in molecular weights from 500 to 40,000. The starting f-caprolac-tone is produced by the peracetic acid oxidation of cyclohexanone as shown in Equation (I). 

The preparation of several N-functionalized benziodazoles derived from natural amino acids has been reported (20030L1583). Acetoxybenzioda-zoles 156 and 157 were synthesized by peracetic acid oxidation of the corresponding 2-iodobenzamides 155 (Scheme 32) and isolated as stable, microcrystaUine solids. Acetoxybenziodazole 156 can be further converted to the tosylate 158 by treatment with p-toluenesulfonic acid or to iodonium... 

Acetaldehyde, first used extensively during World War I as a starting material for making acetone [67-64-1] from acetic acid [64-19-7] is currendy an important intermediate in the production of acetic acid, acetic anhydride [108-24-7] ethyl acetate [141-78-6] peracetic acid [79-21 -0] pentaerythritol [115-77-5] chloral [302-17-0], glyoxal [107-22-2], aLkylamines, and pyridines. Commercial processes for acetaldehyde production include the oxidation or dehydrogenation of ethanol, the addition of water to acetylene, the partial oxidation of hydrocarbons, and the direct oxidation of ethylene [74-85-1]. In 1989, it was estimated that 28 companies having more than 98% of the wodd s 2.5 megaton per year plant capacity used the Wacker-Hoechst processes for the direct oxidation of ethylene. 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

By-product acetic acid is obtained chiefly from partial hydrolysis of cellulose acetate [9004-35-7]. Lesser amounts are obtained through the reaction of acetic anhydride and cellulose. Acetylation of saHcyHc acid [69-72-7] produces one mole of acetic acid per mole of product and the oxidation of allyl alcohol using peracetic acid to yield glycerol furnishes by-product acid, but the net yield is low. 

Fig. 2. Synthesis of uma2enil (18). The isonitrosoacetanihde is synthesized from 4-f1iioroani1ine. Cyclization using sulfuric acid is followed by oxidization using peracetic acid to the isatoic anhydride. Reaction of sarcosine in DMF and acetic acid leads to the benzodiazepine-2,5-dione. Deprotonation, phosphorylation, and subsequent reaction with diethyl malonate leads to the diester. After selective hydrolysis and decarboxylation the resulting monoester is nitrosated and catalyticaHy hydrogenated to the aminoester. Introduction of the final carbon atom is accompHshed by reaction of triethyl orthoformate to...

The ease of oxidation varies considerably with the nature and number of ring substituents thus, although simple alkyl derivatives of pyrazine, quinoxaline and phenazine are easily oxidized by peracetic acid generated in situ from hydrogen peroxide and acetic acid, some difficulties are encountered. With unsymmetrical substrates there is inevitably the selectivity problem. Thus, methylpyrazine on oxidation with peracetic acid yields mixtures of the 1-and 4-oxides (42) and (43) (59YZ1275). In favourable circumstances, such product mixtures may be separated by fractional crystallization. Simple alkyl derivatives of quinoxalines are... 

---