Nitriles alkyl

To explain the experimentally observed high reactivity of HCN and alkyl nitriles under snperacidic condition, Shndo found that in the Gat-terman and Houben-Hoesch reactions, diprotonated HCN (or nitriles) are involved as the de facto reagents (HC N H2, RC N H2). 

Some nitriles are expl, especially if they contain several —CN groups or a combination of —CN and —N02 groups. Other nitriles have been considered for use in double-base propints as they cool the flame and provide longer burning times a variety of alkyl nitriles have been investigated as plasticizers (Ref 7)... 

On the other hand, 3-phenylpropionitrile was synthesized from Z-3-phenyl-propionaldoxime (0.75 M) in a quantitative yield (98gP ) by the use of cells of E. coli JM 109/pOxD-9OF, a transformant harboring a gene for a new enzyme, phenylacetaldoxime dehydratase, from Bacillus sp. strain OxB-1. Other arylalkyl- and alkyl-nitriles were also synthesized in high yields from the corresponding aldoximes. Moreover, 3-phenylpropionitrile was successfully synthesized by the recombinant cells in 70 and 100% yields from 0.1 M unpurified P/Z-3-phenylpropionaldoxime, which is spontaneously formed from 3-phenylpropionaldehyde and hydroxylamine in a butyl acetate/water biphasic system and aqueous phase, respectively. 

Another important click reaction is the cycloaddition of azides. The addition of sodium azide to nitriles to give l//-tetrazoles is shown to proceed readily in water with zinc salts as catalysts (Eq. 11.71).122 The scope of the reaction is quite broad a variety of aromatic nitriles, activated and nonactivated alkyl nitriles, substituted vinyl nitriles, thiocyanates, and cyanamides have all been shown to be viable substrates for this reaction. The reaction of an arylacetylene with an azide in hot water gave 1,4-disubstituted 1,2,3-triazoles in high yields,123 while a similar reaction between a terminal aliphatic alkyne and an azide (except 111 - nitroazidobenzcnc) afforded a mixture of regioisomers with... 

Neat butyronitrile reacted under reflux to give 4-an jno-5-ethyl-2,6-dipropylpyrimidine isolated in 98% yield based on Mg. Similarly, acetonitrile gave 4-amino-2,6-dimethylpyrimidine in 152% yield, based on Mg, after reacting in a sealed tu e at 130° C for 13 h. The reaction appears catalytic with respect to Mg. Treatment of alkyl nitriles with metallic sodium(97) or Grignard reagents(98) is known to produce aminopyrimidines, but there have been no reports of such results by the direct action of metallic magnesium on alkyl nitriles. ... 

Aminoisoxazoles 22 have been synthesized by nucleophilic addition of lithiated alkyl nitriles to a-chloroximes <06OL3679>. The cyclization of oxime dianions with diethyl oxalate afforded isoxazole-5-carboxylates 23 by acid-mediated dehydration of intermediate hydroxyisoxazolines <06S2515>. 

Application of the Ritter reaction conditions on y-hydroxy-a,P-alkynoic esters, 102, produced ethyl 5-oxazoleacetates 103 or y-A-acylamino-P-keto ester 104 by reaction with aryl or alkyl nitriles respectively. The y-A-acylamino-P-keto ester 104 can also be transformed into oxazole derivatives using an additional step involving POCI3 <06TL4385>. 

Szabo S, Gallagher GT. 1984. Effects of alkyl nitriles on the gastrointestinal tract. Surv Synth Path Res 3 11-30. 

On the basis of published data for enthalpies of formation, sublimation, and vaporization, the dissociation enthalpies of terminal N—O bonds, DH°(N—O), in various organic compounds including nitrile oxides, were calculated and critically evaluated (18). The derived DH°(N—O) values can be used to estimate enthalpies of formation of other molecules, in particular nitrile oxides. N—O Bond energy in alkyl nitrile oxides was evaluated using known and new data concerning kinetics of recyclization of dimethylfurazan and dimethylfuroxan (19). 

The addition of sodium azide to nitriles to give IH-tetrazoles is shown to proceed readily in water with zinc salts as catalysts. The scope of the reaction is quite broad a variety of aromatic nitriles, activated and unactivated alkyl nitriles, substituted vinyl nitriles, thiocyanates, and cyanamides have all been shown to be viable substrates for this reaction. 

The syntheses were most successful when a nonpolar protic solvent was used. In this work, a synthesis for the formation of alkyl nitriles with a hydroxy group at the a-position is presented. 

R2 = amine, alkyl, nitrile Scheme 7.13 Halogenation of indoles by tryptophan 7-halogenase. 

Molybdenum pentachloride forms mixed complexes and oxychloride adducts with several donors. Thus, the adducts with pyridine, bipyridyl and alkyl nitriles are MoCl4(py)2, MoCRObipy) and MoCR(RCN)2, respectively. 

Figure 8.1. Relation of solubility parameters (solpars or Hildebrand 8 values) and carbon numbers in various homologous series of solvents. (4) Normal alkanes, (B) normal chloroalkanes, (C) methyl esters, (D) alkyl formates and acetates, (E) methyl ketones, (F) alkyl nitriles, ) normal alkanols, (H) alkyl benzenes, and (I) dialkyl phthalates.

Nitriles are most commonly prepared via the conversion of carboxylic acids to primary amides, followed by dehydration with boiling acetic anhydride, or other commonly employed dehydration reagents, e.g. SOCI2 or POCI3. This is a useful synthesis for amide, because it is not limited by steric hindrance. Alkyl nitriles can be prepared by the action of metal cyanides on alkyl halides (see Section 5.5.2). 

Reductive decyanation. K-A1203 reduces alkyl nitriles in hexane at 25° in 70-90% yield. The reaction is rapid for secondary and tertiary nitriles but requires about 1 hour for primary nitriles. Potassium alone is less efficient. The reaction was useful in a synthesis of the sex pheromone 1. 

Aryl and alkyl nitriles also react with pyrrolyl and indolyl anions to yield the acylated heterocycles (see Section 3.05.1.2.9). 

However, the most important approach to 2-substituted dihydro-1,3-oxazines involves the acid-promoted condensation of alkyl nitriles and propane-1,3-diols, carbonium species (200) are assumed to be intermediates in this reaction, being formed preferentially from the more highly substituted position of the diol (Scheme 87) (57JOC11). 

Ignoring the potential limitations of the dielectric data, we can evaluate the Debye-Onsager model for a number of apparently roughly Debye solvents, like propylene carbonate, the alkyl nitriles, the alkyl acetates, and other solvents. First of all, C( ) is often strongly nonmonoexponential, in contradiction to the theoretical prediction. Second, the observed average solvation time is often much different from xt. 

Reaction XLVIH. (b) Action of Alkali Cyanides on Alkyl Hydrogen Sulphates. (A., 10, 249.)—The alkyl nitriles may also be prepared by dry distilling alkali cyanides with alkali-alkyl-sulphates. 

The preparation of amides by the addition of hydrogen cyanide or alkyl nitriles to alkenes in the presence of acids, known as the Ritter reaction, has been reviewed.229-232 The reaction may be considered simplistically as nucleophilic attack of a nitrile on a carbocation formed by the protonation of an alkene. Subsequent hydrolysis of the nitrilium intermediate gives the amide product (equation 164). The overall result is addition of a molecule of H—NHCOR to a C—C double bond. 

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