New facile method for conversion of oximes to nitriles. Preparation and acid-catalyzed transformation of aldehyde oxime ortho esters

Abstract

Notesated phosphine. A possible sequence of events to account for the product is shown above. The transesterification may occur before or after the ring cleavage. Experimental SectionGeneral. Reactions of phosphines were conducted under nitrogen. Mp values are corrected. Proton nmr spectra were taken with JEOL MH-100 or Varían T-60 spectrometers. Proton-decoupled 31P nmr spectra were taken on a Bruker HFX-10 system at 36.43 MHz; shifts are relative to external 85% H3PO4. The proton-decoupled 13C nmr spectrum was obtained by the Fourier transform technique on the Bruker spectrometer at 22.62 MHz utilizing C6Fe as external heteronuclear lock in a 3-mm coaxial capillary. Analyses were performed by MHW Laboratories, Garden City, Mich.Synthesis of Methyl(4-carboxybutyl)phosphine Oxide (3) from Methyl l-Methylphospholane-2-carboxylate (1). To 30

Recent Advances in Electrochemical Synthesis of Nitriles: A Sustainable Approach

“…Nitriles are obtained from aldoximes using Chlorothionoforrnates, [119] 1,1'-carbonyldibenzotriazole, and 1,1'-sulfonyldibenzotriazole, [120] 1,l -dicarbonylbi-imidazole, [121] the acid-catalyzed reaction of aldoximes and orthoesters, [122] all of which are consist of harsh reaction conditions and damage the environment. Hence it is necessary to design new methods which are benign and environmentally friendly.…”

Nitriles (Cyanides)

“…Oximes may also be converted readily to nitriles by an acid-catalyzed reaction with ortho esters [28]. …”

Dehydration of Aldoximes to Nitriles Using a Polymeric Reagent

“…1 Development of e¤cient, mild and reliable reagents for this propose has been an objective of synthetic chemists and over the years a large number of such reagents have been reported, e.g. Sulfuryl chloride £uoride, 2 chlorosulfonyl isocyanate, 3 diphosphorus tetraiodide, 4 1,1 H -dicarbonylbisimidazole, 5 chlorothionoformate, 6 trimethylamine^sulfur dioxide complex, 7 phosphonitrilic chloride, 8 titanium chloride^pyridine, 9 dialkyl hydrogenphosphonate, 10 ortho ester^acid catalyst, 11 polymer supported triphenyl-phosphine^carbon tetrachloride, 12 N-tri£uoroacetylimidazole, 13 2-methylthio-4,6-diphenyl-pyrylium tetra-£uoroborate^triethylamine, 14 1-chlorosul¢nyl-4-dimethylaminopyridinium chloride, 15 carbon disul¢de^phase transfer catalyst, 16 , CsX^zeolite, 17 , montmorillonite-KSF, 18 , 1,1 Hcarbonyldibenzotriazole, 19 envirocat EPZG, 20 sulfuric acid^silica gel, 21 N,N H -sul¢nylbisimidazole 22 and di-2pyridyl sul¢te. 23 Each method using the above reagents encounters at least one of the following drawbacks: (1) long reaction times, (2) unsatisfactory yields, (3) harsh reaction conditions, (4) expensive or not readily available reagents, (5) inconvenient preparation of reagents, (6) need for addition of an acid or a base, (7) need of a phase transfer catalyst, (8) high reaction temperature, (9) tedious work-up procedures, or (10) limited adaptability both to aryl and alkyl substituted aldoximes.…”