Hydrogen peroxide with nitriles

All of the stereoisomerie methyl 2,3-anhvdro-6-deoxy-DL-hexo-pyranosides have been prepared by epoxidation of 2,3-unsaturated pyranosides (328-331, R = Me) with hydrogen peroxide-benzo-nitrile. The H-n.m.r. data of their 4-O-acetyl derivatives were reported, and discussed in connection with configurational and conformational assignments.223 The1 regio- and stereo-selectivity of the... 

The reaction of alkaline hydrogen peroxide with ogg-unsaturated nitriles was first explored by Murray and Cloke,120 who found that certain of these compounds (Eq. fld), when subjected to the JRadzis-icwBki amidation procedure, yielded a, -epoxyamides instead of the anticipated a t-unB turated amides. 

Oxidation of the Schiff bases (19) made from the monoamide of DAMN (derived from DAMN by hydration of one of the nitrile functions) gives 4-cyanoimidazole-5-carboxamides (20) in good yields ( 70% or more) (Scheme 2.1.7). Such oxidations can be readily accomplished using hydrogen peroxide with a catalytic amount of sodium molybdate fSl]. 

Hydrolysis with powdered potassium hydroxide or potassium fluoride on alumina in r-butyl alcohol converts nitriles to amides without further hydrolysis to carboxlic acids. Under similar conditions, addition of alkyl halides gives iV-alkylcarboxyamides. Less drastic acidic or basic hydrolysis conditions involve disproportionation of alkaline hydrogen peroxide with concomitant hydration of the nitrile (equation 21). 

Singlet oxygen is also formed in the reaction of hydrogen peroxide with bromine [412]. McKeown and Waters [411, 412] found that peracids and nitriles evolve singlet oxygen in the presence of hydrogen peroxide. 

Xu Q, Zhu JJ, Hu XY (2007) Ordered mesoporous polyanifine film as a new matrix for enzyme immobilization and biosensor construction. Anal Chun Acta 597(1) 151—156 Yakovleva J, Davidsson R, Lobanova A et ak (2002) Enzyme immunoassay using silicon microchip with immobilized antibodies and chemiluminescence detection. Antd Chem 74(13) 2994—3004 Yamada H, Kobayashi M (1996) Nitrile hydiatase and its application to industrial production of acrylamide. Biosci Biotechnol Biochem 60 1391—1400 Yamamoto K, Ohgam T, Torimura M et al. (2000) Highly-sensitive flow injection determination of hydrogen peroxide with a peroxidase-immobilized electrode and its application to clinical chemistry. Anal Chim Acta 40(2) 201—207... 

Hydrazones stemming from aldehydes are easily converted into nitriles. For example, when treated with alkylating agents hydrazones form hydrazonium salts [232], which upon ehmination give nitriles as the formally oxidized products. Alternatively, hydrazones can be oxidized directly, and for this reaction oxidants such as peracids [233], oxone [234] and dioxirane [235] were found to be effective. Finally, catalytic systems based on combinations of hydrogen peroxide with metal catalysts [236] or selenium compounds [237] have been developed for this process. Other reactions along these lines include oxidations of monohydrazones giving diazo compounds [238] or nitrilimines [239] and conversions of vicinal dihydrazones into alkynes [240]. 

B). Many nitriles when treated with hydrogen peroxide in warm alkaline solution undergo hydrolysis to amides which can thus be readily obtained in high yield. Insoluble liquid nitriles can be treated directly in the aqueous suspension, but for insoluble solid nitriles the addition of a suitable organic solvent to give a complete solution may be desirable, although the completion of the hydrolysis may not then be so readily detected. 

Weak to moderate chemiluminescence has been reported from a large number of other Hquid-phase oxidation reactions (1,128,136). The Hst includes reactions of carbenes with oxygen (137), phenanthrene quinone with oxygen in alkaline ethanol (138), coumarin derivatives with hydrogen peroxide in acetic acid (139), nitriles with alkaline hydrogen peroxide (140), and reactions that produce electron-accepting radicals such as HO in the presence of carbonate ions (141). In the latter, exemplified by the reaction of h on(II) with H2O2 and KHCO, the carbonate radical anion is probably a key intermediate and may account for many observations of weak chemiluminescence in oxidation reactions. 

This type of amination by an oxaziridine is assumed to be the key step of a novel process for hydrazine manufacture, in the course of which butanone in solution with ammonia is reacted with hydrogen peroxide and acetonitrile. The smooth formation of oxaziridines from Schiff bases and hydrogen peroxide-nitrile mixtures is as well known as NH transfer from an oxaziridine like (300), suggesting the intermediacy of (300) as the N—N forming agent (72TL633). 

Hydrogenated nitrile rubbers were introduced in the mid-1980s as Therban by Bayer. The initial grade had an acrylonitrile content of only 17% instead of approx. 34% in conventional NBR. Whilst non-sulphur-curing systems such as the use of peroxides with triallyl cyanurate or isocyanurate are necessary, the saturated rubber has a number of advantages over NBR. These include improved... 

It was found inadvisable to use more than four molecules of form-amide [ (47) when R = H] per molecule of anthranilic acid and the condensation produces best results when the mixture is heated at 120 -130°C for 2 hr followed by further heating at 170°-180 C for 2 hr. Other variants of this reaction involve the use of ammonium o-acylaminobenzoates, anthranilic acid in the presence of nitriles and acetic anhydride, o-acetamidonitrile with acetic anhydride or hydrogen peroxide, anthranilic esters and aliphatic or aromatic amides or amidines, isatoic anhydride with amides or amidines, and anthranilic esters with aryl iminochlorides in acetoned The mechanism proposed by Bogert and Gotthelf has had experimental supporR and is represented in Scheme 12. 

Although the biosynthetic cascade hypothesis predicts the co-occurrence of endiandric acids D (4) and A (1) in nature, the former compound was not isolated until after its total synthesis was completed in the laboratory (see Scheme 6). Our journey to endiandric acid D (4) commences with the desilylation of key intermediate 22 to give alcohol 31 in 95% yield. The endo side chain is then converted to a methyl ester by hydrolysis of the nitrile to the corresponding acid with basic hydrogen peroxide, followed by esterification with diazomethane to afford intermediate 32 in 92% overall yield. The exo side chain is then constructed by sequential bromination, cyanide displacement, ester hydrolysis (33), reduction, and olefination (4) in a straight-... 

A milder procedure involves the reaction of a nitrile with an alkaline solution of hydrogen peroxide.147 The strongly nucleophilic hydrogen peroxide adds to the nitrile and the resulting adduct gives the amide. There are several possible mechanisms for the subsequent decomposition of the peroxycarboximidic adduct.148... 

Incompatibility of the nitrile group with the oxidative work-up of the L-Selectride reduction using basic hydrogen peroxide Significant hydrolysis to the primary amide with concomitant exothermic activity and loss of product... 

A solid-phase synthesis of 3-substituted isoxazoles 31 in good yields and purities was achieved by 1,3-DC of polymer-supported vinyl selenide with in situ generated nitrile oxides treatment of intermediate isoxazolines 30 with an excess of hydrogen peroxide resulted in the release of isoxazoles 31 while the use of Mel/Nal led to 3-substituted 5-iodoisoxazolines... 

The oxidation of thioamides 63 with a wide variety of oxidizing agents is a well-employed method for the synthesis of 3,5-disubstituted-l,2,4-thiadiazoles 64 <1982AHC285>. However, this method is limited mainly to arylthioamides. The most common oxidizing agents tend to be halogens, hydrogen peroxide, dimethyl sulfoxide (DMSO), and nitrous acid. Yields from these reactions are variable and depend on the thioamide, oxidant, and conditions used (Equation 19). By-products such as nitriles and isothiocyanates are usually formed. 

Aldehyde 26 was treated with hydroxylamine hydrochloride in refluxing methanol to give a mixture of (E)- and (Z)-pyrrolotriazine 40 in 59% and 21% yield, respectively. Dehydration of aldoxime 40 with trifluoromethanesulfonic anhydride and triethylamine in dichloromethane afforded triazine 41. Conversion of the nitrile 41 to the deprotected amide 42 was accomplished in 96% yield on treatment of 41 with basic hydrogen peroxide in ethanol <2001CAR77>. 

---