Ketone Amidations

DMSO, NaCN, 125-180°, 5-48 h, 65-90% yield.This cleavage reaction is successful for aromatic systems containing ketones, amides, and carboxylic acids mixtures are obtained from nitro-substituted aromatic compounds there is no reaction with 5-methoxyindole (180°, 48 h). 

The general method for preparation of heterocyclic enamino ketones, amide vinylogs, consists of a cyclization reaction (Scheme 6). The most convenient technique involves heating the starting substance in acetonitrile in the presence of silver perchlorate 137-139). 

Aldehydes and carboxylic acids having IC atom more than R, as well as ketones, amides and esters can be prepared similarly, the rertction always proceeding in the ditecdon predicted for potential carbanioo attack on the unsaturated Catom ... 

Acid chlorides are easily detected by their characteristic absorption near 1800 cm-1. Acid anhydrides can be identified by the fact that they show two absorptions in the carbonyl region, one at 1820 cm 1 and another at 1760 cm-1. Esters are detected by their absorption at 1735 cm 1, a position somewhat higher than that for either aldehydes or ketones. Amides, by contrast, absorb near the low wavenumber end of the carbonyl region, with the degree of substitution on nitrogen affecting the exact position of the IR band. 

Nitrogen compounds, reduction, 103-104 N-(exo-2-Norbornyl)acetamide, ketone amidation, 130 Nucleophilic species ... 

Dithiophosphoric acids, (RO)2PS2H, have been used for the thionation of carbonyl groups in certain aldehydes, ketones, amides, esters, thio-carboxylates and other organics.163 The mechanism for this reaction proceeds via a reversible nucleophilic attack of the thioacid on the carbonyl compound, which can then rearrange by way of a four-membered PSCO cyclic intermediate into the desired C=S containing molecule and thiophosphoric acid (Equation 81).163... 

Bis-(4-methoxyphenyl)-[l,3,2,4]dithiadiphosphetane 2,4-disulfide, transforms the carbonyl groups of ketones, amides and esters into the corresponding thiocarbonyl compounds. Cf. Knorr thiophene synthesis. 

Secondary amides have the advantage over tertiary amides that they are relatively easy to remove. It is quite difficult to stop the addition products from aldehydes, ketones, amides, epoxides and nitriles cyclizing directly to give a variety of lactone derivatives (by attack of OH on the secondary amide) or lactam derivatives (by attack of the secondary amide on the new electrophihc centre). Thioamides behave similarly . 

Group-transfer polymerizations make use of a silicon-mediated Michael addition reaction. They allow the synthesis of isolatable, well-characterized living polymers whose reactive end groups can be converted into other functional groups. It allows the polymerization of alpha, beta-unsaturated esters, ketones, amides, or nitriles through the use of silyl ketenes in the presence of suitable nucleophilic catalysts such as soluble Lewis acids, fluorides, cyanides, azides, and bifluorides, HF. ... 

The fluorination of enolates of ketone, amide, or hydrazone bearing a chiral auxiliary (SAMP, Evans oxazolidine) with nonchiral fluorination reagent (A-fluoro sulfonimides, A-fluoropyridine) occurs with excellent diastereoselectivities. ... 

In the presence of several equivalents of N-F-type reagents, " it is possible to perform the difluorination of enolates of ketones, amides, and enamines. The difluorination of nucleosides has also been performed with Selectfluor (Figure 2.11). ... 

The CM of olefins bearing electron-withdrawing functionalities, such as a,/ -unsaturated aldehydes, ketones, amides, and esters, allows for the direct installment of olefin functionality, which can either be retained or utilized as a synthetic handle for further elaboration. The poor nucleophilicity of electron-deficient olefins makes them challenging substrates for olefin CM. As a result, these substrates must generally be paired with more electron-rich crosspartners to proceed. In one of the initial reports in this area, Crowe and Goldberg found that acrylonitrile could participate in CM reactions with various terminal olefins using catalyst 1 (Equation (2))." Acrylonitrile was found not to be active in secondary metathesis isomerization, and no homodimer formation was observed, making it a type III olefin. In addition, as mentioned in Section 11.06.3.2, this reaction represents one of the few examples of Z-selectivity in CM. Subsequent to this report, ruthenium complexes 6 and 7a were also observed to function as competent catalysts for acrylonitrile... 

Organic carbonyl compounds—aldehydes, ketones, amides, and acyl halides—in which the carbonyl group is not part of a cyclic structure have interesting conformational properties that may differ widely according to the molecular system bearing these substituents. 

The present report gives the methods used and the data obtained for acid, ester, aldehyde, ketone, amide, hydroxyl, and ether functional groups in kero-gen and trona acids. These methods may be applicable also in studying coals and other carbonaceous materials. 

Phenol Carbazole ylic Acid Ketone Amide Sulfoxide Total... 

Thus the angle becomes greater in the series of carbonyl compounds—ketone, amide, ester and carboxylate anion. 

Similar reaction conditions allowed the preparation of a-branched nitriles (Fig. 83). When mono-, di-, and trisubstituted olefins 355 bearing functionalities, such as esters, aldehydes, ketones, amides, or alcohols, were reacted with tosyl cyanide 356 and phenylsilane in the presence of 1 mol% of the (salen)Co catalysts 357a or 357b the corresponding nitriles 358 were isolated in 55-99% yield (entry 21) [402]. Although no mechanistic evidence was provided, the reaction may be assumed to proceed similarly as the hydroazidation. 

Hydrosilylation of Ketones, Amides, Imides and Related Compounds.232... 

Fig. 14.50. Crossed McMurry reactions ketone/ester coupling (top) and ketone/amide coupling (bottom).

The selective activation of propargylic alcohols by [Cp RuCl(/u,2-SR)2 RuCp Cl] complexes (R = Me, lPr) in the presence of NH4BF4, promotes the nucleophilic substitution of the hydroxy group by various carbon nucleophiles such as ketone, amides and alkenes (Schemes 47-49) [101]. 

Iron(III) chloride, and other simple salts, react with a range of organic ligands such as alcohols, ethers, aldehydes, ketones, amides, sulfoxides, amine and phosphine oxides, etc. The structures of many of these complexes are unknown some appear to be simple addition compounds while others have salt structures. 

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