Oxidation amide

CCls CHO. A colourless oily liquid with a pungent odour b.p. 98°C. Manut actured by the action of chlorine on ethanol it is also made by the chlorination of ethanal. When allowed to stand, it changes slowly to a white solid. Addition compounds are formed with water see chloral hydrate), ammonia, sodium hydrogen sulphite, alcohols, and some amines and amides. Oxidized by nitric acid to tri-chloroethanoic acid. Decomposed by alkalis to chloroform and a methanoate a convenient method of obtaining pure CHCI3. It is used for the manufacture of DDT. It is also used as a hypnotic. 

The performance of AOS vs. the other surfactants was tested with three foam boosters, namely, amide oxide (AO), lauryl myristic monoethanol amide (LMMEA), and coco diethanolamide (coco DEA) at 90 10 anionic/booster ratio. Blends were evaluated at 0.025% active, 41 °C, and 140 ppm vegetable shortening oil. The results in Fig. 21 show that AOS blends outperform the reference standard whereas the other blends were of equal or less performance. The AOS/LMMEA blend gave superior performance. It was further shown that the addition of a small amount of AES (10% on total actives) further enhanced the performance of the AOS system (see Fig. 22). AOS when formulated with AES and amide therefore has outstanding dishwashing performance and is an attractive candidate for use in formulating light-duty liquids. 

Rapid interaction at —70°C/1 mbar causes ignition. Slow interaction produced a solid which exploded at 206° C, probably owing to formation of ruthenium amide oxide or ruthenium nitride. 

In contrast to aminoperoxyl radicals, amidoperoxyl radicals do not decompose with the formation of H02 radicals [2], According to this scheme the rate of amides oxidation obeys the following equation (at [02] > 10-4mol L 1) ... 

Halophenols are easier to dispose of by extraction. Chlorophenyl esters are resistant to hydrogenation and are hence compatible with benzyloxycarbonyl. Benzotriazolyl esters are unique in that they exist in two different forms (see Section 7.17). They are too reactive for routine use but are often employed without isolation after their preparation, using a carbodiimide or other (see Section 7.20). An exception to this are the benzotriazolyl adducts of. V-lrilylamino acids that are amide oxides (see Section 7.17), which are stable to aqueous sodium hydroxide but undergo aminolysis normally. 

Sequential Amide Oxidation - Olefin Metathesis Strategies. 306... 

This idea is perhaps easiest to illustrate for the oxidation of an amide (Scheme 1). Amide oxidation reactions are of tremendous synthetic interest because they can provide an oxidative alternative to the synthesis of reactive N-acyliminium ion intermediates (3). Such a route would complement well the existing reductive and condensation-based approaches [1-3]. However, because amides... 

While anodic amide oxidations have found the most synthetic use to date, the oxidation of nitrogen-containing molecules is not limited to amide substrates. A variety of amine oxidations have been studied, and the Kolbe electrolysis of carboxylic acids has been used to generate nitrogen-based reactive intermediates. Many of these reactions also offer unique synthetic advantages (Sects. 10.2 and 10.3). 

One of the most practical applications of the anodic amide oxidation reaction... 

Anodic amide oxidations have also proven useful for selectively converting amides into enamides that have in turn been used to functionalize the carbon beta to nitrogen. For example, the four-electron oxidation of carbamates was used to introduce a carbonyl beta to a nitrogen (Scheme 21) [50]. In this example, the starting carbamate was oxidized at a carbon... 

In a related set of reactions, anodic amide oxidation reactions have been... 

In addition to using indirect oxidation reactions, electroauxiliaries have been used to circumvent problems with problematic amide oxidations. As mentioned in Sect. 10.2.2, an electroauxiliary is a group that is added to a molecule in order to reduce the oxidation potential of the... 

In addition to silicon, sulfur groups have been used as auxiliaries for amide oxidation reactions (Scheme 31) [63], However, in these cases the mechanism of the reaction is different. The sulfur is oxidized to form a sulfur radical cation that is then eliminated from the molecule in order to... 

The Application of Amide Oxidations to the Synthesis of Natural Products I 297... 

Because anodic amide oxidation provides an excellent method for functionalizing... 

Shono and coworkers have used a pair of amide oxidation reactions to synthesize the naturally occurring alkaloid Anatoxin A [77]. As illustrated in Scheme 41, the synthesis used the first anodic amide oxidation to functionalize... 

In many of the direct amide oxidations illustrated above, the reactions were used to functionalize amino acid derivatives. Because of the reactions effectiveness in this area, anodic electrochemistry has proven to be an outstanding tool for building constrained peptidomimetics [78-81]. In this work, a series of constrained peptide analogs were designed by replacing spatially close hydrogens in a proposed... 

Scheme 46 Sequential amide oxidation-olefin metathesis strategy.

The use of an anodic amide oxidation to introduce a vinyl group to the C5 position of a proline derivative has proven to be an effective strategy for building other constrained peptidomimetics as well. For example, a variation on the approach has... 

In addition to demonstrating the utility of anodic amide oxidations as a tool for... 

Direct electrochemical amide oxidation reactions have also been employed in parallel synthesis using a spatially addressable electrochemical platform [107]. In this work, an electrolysis platform was set up so that 16 electrochemical reactions could be run in parallel at the same time. The cells were set up in a 4 by 4 array in which each cell was equipped with a... 

Bicyclic [33] and 7,5-bicyclic [34, 35] dipeptides (Scheme 24) have been syn-thetized by a one-step electrochemical cyclization from various dipeptides. The selective anodic amide oxidation... 

Chemoselective anodic methoxylation at a distinct carbon atom in the a-position to an amino group in a polypeptide was achieved by prior introduction of a silyl group as an electroauxiliary at this carbon atom [156]. Amide oxidation in A-acetylpyrrolidines substituted with electron-rich phenyl rings led to either methoxylation a to the nitrogen atom or in the benzylic position. Mechanistic studies indicate that both the amide and the phenyl oxidation compete, but intramolecular electron transfer leads to... 

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