Cyanides alkyl

Aliphatic nitriles (or alkyl cyanides) can be prepared by the following methods ... 

By hydrolysis of alkyl cyanides (or nitriles) with alkali hydroxide solutions, for example ... 

For those nitriles which yield water-insoluble amides e.g., the higher alkyl cyanides), hydrolysis to the amide often leads to a satisfactory derivative. The hydration is eflfected by warming a solution of the nitrile in concentrated sulphuric acid for a few minutes, cooling and pouring... 

Cyanide ion ( C = N ) The negatively charged carbon atom of cyanide ion IS usually the site of its nucleophilic character Use of cyanide ion as a nucleophile permits the extension of a carbon chain by carbon-carbon bond formation The product is an alkyl cyanide or nitrile... 

The large rate enhancements observed for bimolecular nucleophilic substitutions m polai aprotic solvents are used to advantage m synthetic applications An example can be seen m the preparation of alkyl cyanides (mtiiles) by the reaction of sodium cyanide with alkyl halides... 

A second factor that can tip the balance m favor of substitution is weak basicity of the nucleophile Nucleophiles that are less basic than hydroxide react with both pri mary and secondary alkyl halides to give the product of nucleophilic substitution m high yield To illustrate cyanide ion is much less basic than hydroxide and reacts with 2 chlorooctane to give the corresponding alkyl cyanide as the major product... 

Primary and secondary alkyl halides may be converted to the next higher carboxylic acid by a two step synthetic sequence involving the preparation and hydrolysis of nitriles Nitnles also known as alkyl cyanides are prepared by nucleophilic substitution... 

Nitrile groups m cyanohydrins are hydrolyzed under conditions similar to those of alkyl cyanides Cyanohydrin formation followed by hydrolysis provides a route to the preparation of a hydroxy carboxylic acids... 

Substitutive lUPAC names for nitriles add the suffix nitrile fo fhe name of fhe parenf hydrocarbon chain fhaf includes fhe carbon of fhe cyano group Nifriles may also be named by replacing the ic acid or oic acid ending of the corresponding carboxylic acid with omtrile Alternatively they are sometimes given functional class lUPAC names as alkyl cyanides... 

Isoquinoline also forms Reissert compounds when treated with benzoyl chloride and alkyl cyanide (28), especially under phase-transfer conditions (29). The W-phenylsulfonyl Reissert has been converted to 1-cyanoisoquinoline with sodium borohydride under mild conditions (154). When the AJ-benzoyl-l-alkyl derivative is used, reductive fission occurs and the 1-alkyLisoquinoline is obtained. 

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... 

Nitriles, or alkyl cyanides, are compounds in which carbon is bound to nitrogen by triple bonds. They tend to be stable, neutral substances with pleasant smells and are less toxic than hydrogen cyanide. The smallest compounds are water soluble liquids and all are soluble in organic solvents. 

Hydrocarbon Gngnard reagents give the alkyl cyanides, whereas perfluo-rinated Grignard reagents produce the sulfides This reaction is useful for the preparation of alkyl perfluoroalkyl sulfides to the exclusion of di and polysulfides, which are produced by other methods... 

Acetonitrile.—The various reactions by which the nitriles or alkyl cyanides are obtained have already been mentioned m one or other of the previous notes, but they may be recapitulated. 

A common method for the preparation of alkyl cyanide 2 is the treatment of corresponding alkyl halides 1 with cyanide. The corresponding reaction with aromatic substrates is called the Rosenmund-von-Braun reaction. 

Cyan-, of or combined with cyanogen, cyano-(as Cyanpropionadure, cyanopropionic acid), cyanide of (as Cyanammonium, ammonium cyanide), -alkali, n. alkali cyanide, -alkyl, n. alkyl cyanide. 

Vinylic copper reagents react with CICN to give vinyl cyanides, though BrCN and ICN give the vinylic halide instead." Vinylic cyanides have also been prepared by the reaction between vinylic lithium compounds and phenyl cyanate PhOCN." Alkyl cyanides (RCN) have been prepared, in varying yields, by treatment of sodium trialkylcyanoborates with NaCN and lead tetraacetate." Vinyl bromides reacted with KCN, in the presence of a nickel complex and zinc metal to give the vinyl nitrile. Vinyl triflates react with LiCN, in the presence of a palladium catalyst, to give the vinyl nitrile." ... 

The first recorded correlation of dipole moments with substituent constants was observed by Taft (3), who reported results for alkyl cyanides, chlorides, iodides, and tertiary amines. Kross and Fassel (31) have reported the correlations of dipole moments for 4-substituted nitrobenzenes with the simple Hammett equation. Rao, Wohl, and Williams (32) have studied the correlation of dipole moments of disubstituted benzenes with eq. (1) and of monosubstituted benzenes with the equation... 

B. From Cyano-compounds and Phosphorus(v) Halides.—Continued reports of the reactions of alkyl cyanides with phosphorus pentachloride appear. With dicyanides the formation of phosphazenes occurs via a series of intermediates whose stability varies with the nature of X ... 

R3N — C5H5N — RC=N , the unshared pairs are in sp3, sp2 and sp1 orbitals, respectively, and the declining basicity is reflected in the two pKa values quoted above, and in the fact that the basicity of alkyl cyanides is very small indeed (MeCN, pR = -4-3). 

The alkyl halides react with cyanide to produce alkyl cyanides. But this reaction has rarely been employed to obtain the increased length of the chain because of the long reaction times and poor yields. However, the use of DMSO as a solvent has simplified the procedure and improved the yields for the conversion of primary and secondary alkyl chlorides into cyanides, without any rearrangement. 

Fluorinated alkyl cyanides, such as trifluoroacetonitrile, pentafluoropropionitrile, per-fluorobutyronitrile and chlorodifluoroacetonitrile, react with butadiene in the gas phase at 350-400 °C to afford pyridines in high yields (equation 82)72. The push-pull diene 150 and electron-rich cyanides (acetonitrile or acrylonitrile) furnish pyridines (equation 83)73. 

Acetone cyanhydrin has been used as a convenient source of cyanide ion for the preparation of alkyl cyanides (6.1.1.E) [21]. Moderate yields (50-77%) have been achieved using tetra-n-butylammonium cyanide or hydroxide as the base. 

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