Nitriles iminoesters

Nitriles react with alcohols in the presence of hydrochloric acid to form iminoester hydrochlorides, which are hydrolyzed to the esters (Pinner synthesis). Heitz and coworkers [21-23] published several fine papers on the polyazoester synthesis from the reaction of a series of poly(oxyethylene) glycol or poly(oxypropylene) glycol and AIBN in the presence of dry hydrochloric acid at 0-5°C according to Pinner synthesis. Condensation reactions of ACPC and dihydroxy terminated poly(oxy-ethylene) glycol yield polyazoesters [24,25]. 

Imidates 60 were prepared in two steps by first reacting nitrile derivatives with various alcohols. The condensation of the obtained iminoester with appropriate acetyl chloride resulted in the formation of the title compounds 60a-c (Scheme 12). The structures of the products 60 were elucidated by means of spectroscopic analysis. 

The addition of HC1 to a mixture of an alcohol and a nitrile in the absence of water leads to the hydrochloride salt of the iminoester (27) (Reaction XXI). 

Compounds (82)-(84) were synthesized as outlined in Scheme 3.12. Reaction of naltrexone with 4-hydrazinobenzonitrile [143] under Fischer indole conditions afforded the 5 -nitrile (86) which was catalytically hydrogenated to the primary amine (87) using Raney nickel. The amidines (82)-(84) were prepared by reacting amine (87) with the appropriate iminoester [144, 145],... 

Irradiation of W10O324 or PW12O403, alkanes, and methyl cyanoformate in MeCN solution produces either the corresponding nitriles or a-iminoesters with high selectivity, depending on the temperature, via a mechanism involving two roles for the polyoxotungstate Initial report on sub- 378... 

The synthesis of orthoesters from nitriles 12 is another example of acid-catalyzed etherification. In this reaction, a nitrile is treated with dry hydrogen chloride and an alcohol to form an iminoester hydrochloride. The dry iminoester hydrochloride is then allowed to react with an alcohol and an orthoester is produced. A possible mechanism for the reaction is the following ... 

V-Aminoazoles, for instance 1, react with nitriles or iminoesters to yield amidines 294 (69JPR477 71JPR768). The latter compounds were also obtained on amination of the Schiff bases with potassium amide in liquid ammonia (70JPR669). 

The hydrolysis of coordinated nitriles has recently attracted some attention. A very facile hydrolysis of nitriles to the corresponding amides at platinum(IV) centers has been described.The complex [Cu(H2NCOCH2CONHNH2)Cl] is formed from the reaction NCCH2CONHNH2 the copper(II) both promotes the hydrolysis and is reduced to copper(I). The hydrolysis of 2-cyanopyridine to 2-pyridinecarboxamide is accelerated several hundred times by the copper(II) complexes of the ligands (21) and (22). In the case of the (22) some picolinic acid was formed, resulting from the intramolecular attack of alkoxide to yield an intermediate iminoester. ... 

Related reactions at platinum(II) centers involve the methanolysis of cis- or tra/i5-[PtCl2(PhCN)2] to yield various isomers of the iminoester complexes [PtCl2LL ] (L or L = PhCN or MeO(Ph)C=NH). The reaction of the same nitrile complex with lithium phenylamidate yields the triazadiketonate analog (23). 

Aminoethers Iminoesters Iminolactones Nitrile oxides Nitrones... 

In 1998, Herrmann et al. reported the synthesis of the first chiral carbene containing an oxazoline unit. In this bidentate ligand, the oxazoline ring is linked in its 2-position to the imidazole ring via a methylene bridge [48]. The key step in the synthesis of the imidazolium precursor is the acid-catalyzed cyclization of the oxazoline by reaction of an iminoester, formed in situ from a nitrile function, and the amino alcohol (Scheme 15.12). 

Triazoles. Ethyl benzimidate hydrochloride and semicarbazide hydrochloride refluxed 1 hr. in pyridine 3-hydroxy-5-phenyl-l,2,4-triazole. Y 83%. F. e., also from nitriles in place of iminoesters, and methods s. H. Weidinger and J. Kranz, B. 96, 1064 (1963) f. heterocyclics s. B. 96, 1049, 1059. 

Hydrobromic acid Carboxylic acid esters and amides from nitriles via iminoester hydrobromides s. 14, 184... 

ENOLETHER ISOL 0-FUNCT CYCLOHEXANE CYCLOALKADIENE N-SULFONYL AZIDE CYCLOPENTANE,- ISOL CYCLOALKENE IMINOESTER + N-SULFONYL C-FUNCT NITRILE... 

By passing dry hydroehloride in alcohol solution of adamantanecarboxylic acid nitrile, Shvekhgeimer and Kuzmicheva [56, 57] have obtained hydrochloride of adamantane carboxylie acid iminoester. After boiling it with equivalent amount of o-phenylenediamine in absolute aleohol area, compound 68 was obtained with yield equal to 72% ... 

Oxamic acid derivatives from cyanoformamide Iminoester hydrochlorides from nitriles... 

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