Alkyl cyanides, synthesis

DL-Alk-2-enopyranos-4-uIose, 2,3-dideoxy-synthesis, 1, 426 Alkoxy nitroxide radicals pyridines ESR, 2, 146 Alkyl cyanides trimerization, 3, 503 Alkylating agents as pharmaceuticals, 1, 157 Alkylation... 

Niobium, tris(diethyldilhiocarbamato)oxy-stereochemistry, 1,82 structure, 1, 83 Niobium, tris(oxa ato)oxy-stereochcmistry, 1, 82 Niobium, tris(phcnylcncdirhio)-structure, 1, 63 Niobium alanate, 3, 685 Niobium complexes alkyl alkoxy reactions, 2, 358 amides, 2,164 properties, 2, 168 synthesis, 2, 165 applications, 6,1014 carbamicacid, 2, 450 clusters, 3, 672,673,675 hexamethylbenzene ligands, 3, 669 cyanides synthesis, 2, 9 p-dinitrogen, 3, 418 fluoro... 

In this context it is interesting to note that benzonitrile, Ph—C=N, trimerizes to a triazine on a Raney nickel surface. It was assumed that Jt-bonded nitriles were involved in the reaction mechanism.10 This reaction resembles the well-known template synthesis of phthalocyanine complexes from phthalodinitrile. Formation of linear polymers [—C(R)—N—] occurs on heating aryl or alkyl cyanides with metal halides.11... 

The preferred catalysts for the one-step co-cyclization of acetylene and acetonitrile (or alkyl cyanides in general) to give a-picoline (or 2-alkylpyridines) are i/ -Cp-cobalt cod or / -trimethylsilyl-Cp-cobalt cod (eq. (2)). The a-picoline synthesis is best performed in pure nitrile without any additional solvent [5 d]. 

The most important synthesis is the acid-catalysed cyclocondensation of alkyl cyanides with propanediols, e.g. 13 ... 

The large rate enhancements observed for bimolecular nucleophilic substitutions in polar aprotic solvents offer advantages in synthesis. One example is the preparation of alkyl cyanides (nitriles) by the reaction of sodium cyanide with alkyl halides ... 

Alkyl cyanides are generally made from the corresponding alkyl halide (usually primary) and sodium cyanide by an Sfj2 displacement, as shown in this synthesis of an acid ... 

Many phase transfer processes are conducted in the absence of solvent. The early ester formation reactions, for example, were carried out with solid carboxylate salt in the presence of a mixture of alkyl halide and a small amount of tertiary amine [14a]. (It was not until the efficacy of sodium iodide as a cocatalyst was demonstrated that 2-butanone was added as cosolvent [14b].) In Starks synthesis of alkyl cyanides by direct displacement of halide, no organic cosolvent was present [10]. Numerous other examples are recorded. Nevertheless, it is common to conduct a phase transfer reaction in the presence of an organic solvent or cosolvent, particularly if the substrate is a solid. 

Nitdles may be prepared by several methods (1). The first nitrile to be prepared was propionitdle, which was obtained in 1834 by distilling barium ethyl sulfate with potassium cyanide. This is a general preparation of nitriles from sulfonate salts and is referred to as the Pelou2e reaction (2). Although not commonly practiced today, dehydration of amides has been widely used to produce nitriles and was the first commercial synthesis of a nitrile. The reaction of alkyl hahdes with sodium cyanide to produce nitriles (eq. 1) also is a general reaction with wide appHcabiUty ... 

Contents Introduction and Principles. - The Reaction of Dichlorocarbene With Olefins. - Reactions of Dichlorocarbene With Non-Olefinic Substrates. -Dibromocarbene and Other Carbenes. - Synthesis of Ethers. - Synthesis of Esters. - Reactions of Cyanide Ion. - Reactions of Superoxide Ions. - Reactions of Other Nucleophiles. - Alkylation Reactions. - Oxidation Reactions. - Reduction Techniques. - Preparation and Reactions of Sulfur Containing Substrates. -Ylids. - Altered Reactivity. - Addendum Recent Developments in Phase Transfer Catalysis. 

Silver cyanide, reaction with alkyl halides in synthesis of iso-cyamdes, 46, 77... 

In asymmetric Strecker synthesis ( + )-(45,55 )-5-amino-2,2-dimethyl-4-phenyl-l,3-dioxane has been introduced as an alternative chiral auxiliary47. The compound is readily accessible from (lS,25)-2-amino-l-phcnyl-l,3-propancdioI, an intermediate in the industrial production of chloramphenicol, by acctalization with acetone. This chiral amine reacts smoothly with methyl ketones of the arylalkyl47 or alkyl series48 and sodium cyanide, after addition of acetic acid, to afford a-methyl-a-amino nitriles in high yield and in diastereomerically pure form. 

Pyruvic acid is the simplest homologue of the a-keto acid, whose established procedures for synthesis are the dehydrative decarboxylation of tartaric acid and the hydrolysis of acetyl cyanide. On the other hand, vapor-phase contact oxidation of alkyl lactates to corresponding alkyl pyruvates using V2C - and MoOa-baseds mixed oxide catalysts has also been known [1-4]. Recently we found that pyruvic acid is obtained directly from a vapor-phase oxidative-dehydrogenation of lactic acid over iron phosphate catalysts with a P/Fe atomic ratio of 1.2 at a temperature around 230°C [5]. 

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