Nitriles functional group

Here is a list of all dangerous reactions that are related to nitrile functional group behaviour. By active polymerisation is meant the polymerisation that affects the carbon-nitrogen triple bond. Polymerisations that are related to an ethylene double bond will be dealt with on p.336. So far as stability is concerned, it is difficult to say whether certain spontaneous reactions of certain nitriles are... 

The butadiene (80%)-acrylonitrile(17%)-aerylamidoxime(3%) terpolymer was prepared by reacting 2.5g butadiene 80%)-acrylo-nitrile(20%) copolymer (Aldrich) in 150 ml xylene with 1.61g hydro-xylamine hydrochloride in 12 ml n-butanol (freed of HC1 immediately before addition by method of Hurd (4) by dropwise addition under nitrogen. Reaction time and temperature were 23 hr. and 90-95°C. The polymer product was worked up by slowly adding the reaction mixture to 500 ml ether with rapid stirring. The precipitated polymer was allowed to settle, the supernate decanted and the polymer resuspended and washed with two 100 ml portions of ether followed by vacuum drying. Yield 2.04g (81%). Conversion of nitrile functional groups to amidoxime groups was 15% by infrared absorption. 

Number of carbons (including the acyl carbon) Systematic prefix Accepted prefix for acyl and nitrile functional groups... 

Cyanobenzotriazole is readily prepared in 92% yield by treatment of benzotriazole with sodium hydride followed by cyanogen bromide. This solid and stable compound is a convenient reagent for introduction of the nitrile functional group into activated methylene compounds RCH2X, via lithiation <2007ARK5>. 

There are two possible condensation reactions for the nitrile. One is nucleophilic reaction of the oxyanion with the carbon of the nitrile functional group. This carbon is activated by nitrogen and by the strongly electron-withdrawing trichloromethyl group. The other possibility, 8 2 displacement of chloride, is ruled out because there are three chlorines and four bonds in the product. After the nucleophilic reaction, a trace of methanol is needed to form a neutral product by protonation of the anion. 

The mechanism of the Strecker reaction has received considerable attention over its lifespan.4 The conversion of a carbonyl compound into an a-amino acid, by this method, requires a two-step process. The first step consists of the three-component condensation of cyanide and ammonia with the carbonyl compound 1 to produce an intermediate, a-aminonitrile 3. The second step involves the hydrolysis of the nitrile functional group to reveal the latent carboxylic acid 4. Whereas the second step is fairly straightforward and can be done under basic or acid conditions, the first step is more involved than one may expect. The widely accepted sequence for the first step is the nucleophilic addition of ammonia to the carbonyl carbon to produce the corresponding imine derivative 2. Once formed, this initial species is captured by the cyanide anion to generate the requisite a-aminonitrile 3. 

The same tendency was also observed in the coupling reactions with a,y -unsaturated nitriles and ketones. Equally good yields were observed in the couplings of alkyl iodides 33 and 34 which contain acetal or nitrile functional groups. 

These results suggest that the biradical formed from photocleavage of thQ S-N bond (Scheme 13) partitions between hydrogen transfer from C-3 to S to yield the thionitrile photocleavage product 53H, which is deprotonated in the basic media, and isomerization to another intermediate, I, which is photochemi-cally and/or thermally converted to the P4 product, 4-phenylthiazole 51. Interestingly, the infrared spectrum of the crude benzylthioether 54 exhibited an absorption band at 2205 cm", as expected for the nitrile functional group in 54, and another band at 2102 cm", suggesting the presence of an isocyanide in the product mixture. 

The nitrile functional group (CN) has a triple bond between the C and the N, which requires a DU of 2. The DU for CgHiyN = 1, so it cannot have a nitrile functional group. 

The nitrile functional group is, formally, a dehydrated primary amide. (In fact, u little-used nitrile synthesis involves amide dehydration ... 

FIGURE 4.2 A correlation chart for carbonyl and nitrile functional groups. 

When the alkyl group attached to the nitrile functional group is a propyl group or some longer hydrocarbon group, the most intense peak in the mass spectrum results from a McLafferty rearrangement ... 

Oral administration exhibited moderate to high toxicity in different species showing LDso within the range 150-750 mg/kg also moderately toxic by dermal absorption such increased toxicity of this compound over other triazines may be attributed to the presence of nitrile functional group in the molecule teratogenic effects in experimental animals persists in the environment. 

Oral toxicity in rates was found to be moderate possibly toxic by other routes of exposures contains a nitrile functional group and is structurally related to cyanazine moderately toxic by skin absorption teratogenic effect in experimental animals. 

Imidazolium salts with a nitrile functional group attached to the alkyl side chain, such as [C3CNCiIm]BF4 (where CsCNCiIm is the l-propylnitrile-3-methylimidazolium cation) and [C3CNCiCiIm]BF4 (where CaCNCiCiIm is the l-propylnitrile-2,3-dimethylimidazolium cation), act as both solvent and ligand for the palladium-catalyzed hydrogenation of cyclohexadiene to cyclohexene. ... 

Formaldehyde dimethylhydrazone readily added to nitro-alkene 21 under neutral conditions and gave branched-derivative 22 as the major diastereomer. The hydrazone group in 22 was further transformed to an aldehyde or nitrile functional group by treatment with ozone or magnesium monoperoxyphthalate, respectively. The same reaction with other sugar nitro-alkenes has been previously described in preliminary form. (See J.-M. Lassaletta and R. Fernandez, Tetrahedron Lett., 1992,32, 3691). ... 

The utihty of CN as a capping agent in a multicomponent-coupUng reaction has only been studied using limited combinations. Judging from the synthetic versatility of the nitrile functional group in products, further study is desired to find new combinations of available components. 

Based on a related mechanistic concept, a transformation of acyl chlorides into nitriles was reported 15 years ago using 2,4-dinitrobenzenesulfonamide 100 under basic conditions fScheme 19.5517 In this reaction, the intermediate sulfonimidamide anion 101 undergoes a Smiles rearrangement, forming the nitrile functional group after SO2 extrusion and loss of the phenolate moiety. 

Rutnakompituk, M. Modification of epoxy-novolac resins with polysiloxane containing nitrile functional groups synthesis and characterization. Eur. Polym. J.. 2005, 41, 1043. 

In effect, the methyl group and the functionalized carbon center are converted to the nitrile functional group. However, as shown by isotope labeling experiments, ammoxidation of a hydrocarbon having an allylic hydrogen produces a symmetric intermediate wherein the nitrile functional group can be incorporated into either end of the allylic intermediate (see below). Thus, ammoxidation reactions can be divided into three major classes. The first is ammoxidation of a methyl group, effectively, to a nitrile functionality. 

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