Peroxytrifluoroacetic acid compounds

PEROXIDES AND PEROXIDE COMPOUNDS - ORGANIC PEROXIDES] (Vol 18) Peroxytrifluoroacetic acid [359-48-8]... 

Nitroso compounds are formed selectively via the oxidation of a primary aromatic amine with Caro s acid [7722-86-3] (H2SO ) or Oxone (Du Pont trademark) monopersulfate compound (2KHSO KHSO K SO aniline black [13007-86-8] is obtained if the oxidation is carried out with salts of persulfiiric acid (31). Oxidation of aromatic amines to nitro compounds can be carried out with peroxytrifluoroacetic acid (32). Hydrogen peroxide with acetonitrile converts aniline in a methanol solution to azoxybenzene [495-48-7] (33), perborate in glacial acetic acid yields azobenzene [103-33-3] (34). 

As peracids are used peracetic acid, peroxytrifluoroacetic acid, m-chloroperben-zoic acid and others. Hydrogen peroxide or a peracid in combination with triflu-oroacetic acid or certain organoselenium compounds have been successfully employed. 

Tertiary alkyl primary amines can be oxidized to nitro compounds in excellent yields with KMn04.39S This type of nitro compound is not easily prepared in other ways. All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyldioxirane.399 Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone,4,111 various peracids,401 including peracetic and peroxytrifluoroacetic acids, f-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds,402 F7-H20-MeCN,41123 and sodium perborate.403... 

Dimethyldioxirane in wet acetone oxidizes isocyanates to nitro compounds (RNCO —> RN02).404 Oximes can be oxidized to nitro compounds with peroxytrifluoroacetic acid, among other ways.398 Primary and secondary alkyl azides have been converted to nitro compounds by treatment with Ph3P followed by ozone.405 Aromatic nitroso compounds are easily oxidized to nitro compounds by many oxidizing agents.4416 OS III, 334 V, 367, 845 VI, 803. 

Similar oxidative rearrangements to produce carbonyl compounds have been carried out with thallium(III) nitrate557 or peroxytrifluoroacetic acid-BF3.558 The Jones reagent (Cr03—H2S04) in the presence of a catalytic amount of Hg(II) is also effective.559 Chromyl chloride oxidation, when combined with reductive workup, is a simple, convenient one-step method to convert 2,2-disubstituted 1-alkenes to aldehydes.560,561... 

Peroxytrifluoroacetic acid is used tor numerous oxidations of saturated hydrocarbons and aromatic compounds It oxidizes alkanes, alkanols, and carboxylic acids with formation of hydroxylation products [29] Oxidabon of cyclohexane with peroxytrifluoroacetic acid proceeds at room temperature and leads to cyclohexyl trifluoroacetate in 75% yield, 1-octanol under similar conditions gives a mixture of isomeric octanediols in 59% yield, and palmitic acid gives a mixture of hydroxypalmitic acids in 70% yield [29]... 

See Peroxytrifluoroacetic acid 4-Iodo-3,5-dimethylisoxazole See other IODINE COMPOUNDS, N—O COMPOUNDS... 

Oxidation of compound (22) with peroxytrifluoroacetic acid gave the corresponding JV(5)-oxide, which reacted with piperidine to give the piperido derivative <85JMC248>. 

The conversion of an amino group into a nitro group can be useful when specific substitution patterns are required. The synthesis of 1,4-dinitrobenzene from 4-nitroaniline is illustrative (Scheme 7.5). Oxidation can be accomplished directly using peroxytrifluoroacetic acid or in two steps using H2SO5 (monoperoxysulfuric acid) and oxidation of the resulting nitroso compound with hydrogen peroxide. Alternatively, the amine can be diazotized in fluoroboric acid and then reacted with sodium nitrite in the presence of copper powder. 

Dichloroquinoline-5,8-dione is converted by peroxytrifluoroacetic acid into the N-oxide in low yield. This compound is also obtainable directly from 8-hydroxyquinoline with a mixture of concentrated hydrochloric and nitric acids (86JMC1329). The 6,7-dichloroquinone reacts also with imidazole to give the disubstituted product (72LA131). 

Hydroxylations of aromatic rings are also achieved via transient esters that are easily hydrolyzed in situ to the corresponding phenols. In this way, anisole and diphenyl ether are oxidized by peroxytrifluoroacetic acid to predominantly ortho-hydroxy compounds in low yields (equation 147) [1118]. 

Whereas peroxyacetic acid oxidizes 2,6-dichloroaniline to 2,6-dichlo-ronitrosobenzene [/5J], peroxytrifluoroacetic acid carries the oxidation to the nitro compound. Refluxing 2,6-dichloroaniline with peroxytrifluoroacetic acid, which is prepared in situ from 90% hydrogen peroxide and trifluoroacetic anhydride in dichioromethane, gives 2,6-dichloronitroben-zene in 89-92% crude yields and 59-73% pure yields [290. 2-Amino-4-methylpyridine treated with 30% hydrogen peroxide in fuming sulfuric acid at 10-25 °C for 50 h yields 68% of 4-methyl-2-nitropyridine [203]. 

Peroxytrifluoroacetic acid is considered the reagent of choice for the direct oxidation of weakly basic primary aromatic amines to nitro compounds. ... 

Several stabilized alkyliodine(ni) dicarboxylates have been reported in the literature. [Bis-(trifluoroacetoxy)iodo]perfluoroalkanes, RfI(C02CF3)2, were originally prepared by Yagupolskii and coworkers in almost quantitative yield by the oxidation of 1-iodoperfluoroalkanes with peroxytrifluoroacetic acid [173]. These relatively stable compounds have found practical application for the preparation of perflu-oroalkyl(phenyl)iodonium salts, which are used as electrophilic lluoroalkylating reagents (FITS reagents) (Section 2.1.9.5) [174]. 

By epoxidation of unsaturated organosilicon compounds by perbenzoic, perphthalic, 40% peracetic acid [4] and peroxytrifluoroacetic acid [4] was shown, that the best epoxidation agent is peroxytrifluoroacetic acid. During epoxidation of 1.1.3.3-tetramethyldivinyldisiloxane and 1.1.3.3.5.5.7.7-octaphenyl-1.7-divinyltetrasiloxane by perbenzoic acid corresponding diepoxyderivatives has been obtained with 60-65% yield. 

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