Nitrile containing compounds

J Brandrup, Peebles LH Jr., On the chromophore of polyacrylonitrile. IV. Thermal oxidation of polyacrylonitrile and other nitrile containing compounds, Macromolecules, 1(1), 64-72, Jan-Feb 1968. 

The reason that cascade reactions on nitrile-containing compounds are not mainstream yet in chemical synthesis is the fact that chiral molecules are mainly used in the pharmaceutical industry, a small and conservative industry because of health care regulations. Enzyme usage in food or detergent appHcations has taken off to much larger volumes, resulting in higher quantities and more... 

The acetoacetic ester condensation (involving the acylation of an ester by an ester) is a special case of a more general reaction term the Claisen condensation. The latter is the condensation between a carboxylic ester and an ester (or ketone or nitrile) containing an a-hydrogen atom in the presence of a base (sodium, sodium alkoxide, sodamide, sodium triphenylmethide, etc.). If R—H is the compound containing the a- or active hydrogen atom, the Claisen condensation may be written ... 

Nitriles contain the —C=N functional group We have already discussed the two mam procedures by which they are prepared namely the nucleophilic substitution of alkyl halides by cyanide and the conversion of aldehydes and ketones to cyanohydrins Table 20 6 reviews aspects of these reactions Neither of the reactions m Table 20 6 is suitable for aryl nitriles (ArC=N) these compounds are readily prepared by a reaction to be dis cussed m Chapter 22... 

Although acetonitrile is one of the more stable nitriles, it undergoes typical nitrile reactions and is used to produce many types of nitrogen-containing compounds, eg, amides (15), amines (16,17) higher molecular weight mono- and dinitriles (18,19) halogenated nitriles (20) ketones (21) isocyanates (22) heterocycles, eg, pyridines (23), and imidazolines (24). It can be trimerized to. f-trimethyltriazine (25) and has been telomerized with ethylene (26) and copolymerized with a-epoxides (27). 

Substrates. Many different types of nitrogen-containing compounds can be hydrogenated to amines, but nitro compounds and nitriles are the most commonly used starting materials. 

The hydrolysis of an organic nitrile, a compound containing a —C=N group, in basic solution, is proposed to proceed by the following mechanism. Write a complete balanced equation for the overall reaction, list any intermediates, and identify the catalyst in this reaction. 

The synthesis of nitrogen containing heterocyclic systems by photocylo-addition processes is virtually limited to examples involving [ 2 + 2] cycloaddition of imines, nitriles, and azo compounds. Successful additions are few in number and the requirements for success uncertain. The reactions do not proceed with the facility with which carbonyl containing compounds undergo photocycloaddition to alkenes to give oxetans, and various explanations have been advanced to account for this observed lack of reactivity.226... 

Unsaturations of hydroxy-containing compounds are reduced on reaction with nitrile oxides such as tetramethyl terephthalonitrile N,N -dioxide (506) or 1,3,5-triethylbenzene-2,6-dicarbonitrile oxide (507). The reaction of a nitrile oxide with terminal unsaturation, associated with the preparation of a poly-ol from propylene oxide, reduces the mono-ol content of the poly-ol composition. Thus, stirring a solution of an ethylene oxide-propylene oxide copolymer with an OH content of 2.39% and vinyl unsaturation of 3.58% in THF with l,3,5-triethylbenzene-2,6-dicarbonitrile oxide for 1 min results in an effective removal of the terminal unsaturation. 

The only cationic surfactant (Fig. 23) found in any quantity in the environment is ditallow dimethylammonium chloride (DTDMAC), which is mainly the quaternary ammonium salt distearyldimethylammonium chloride (DSDMAC). The organic chemistry and characterization of cationic surfactants has been reported and reviewed [330 - 332 ]. The different types of cationic surfactants are fatty acid amides [333], amidoamine [334], imidazoline [335], petroleum feed stock derived surfactants [336], nitrile-derived surfactants [337], aromatic and cyclic surfactants [338], non-nitrogen containing compounds [339], polymeric cationic surfactants [340], and amine oxides [341]. 

The generation of electrophilic carbene complexes in the presence of nitriles or other cyano-group-containing compounds can lead to the formation of nitrile ylides. With acylcarbene complexes the final products are often 1,3-oxazoles [1194], presumably formed by the mechanism sketched in Figure 4.10. 

Some organic nitrogen-containing compounds (nitriles, ni-troalkyls, amides, etc.) are the rare exceptions to this rule. For example, for acetonitrile, c = 36 and rj = 0.3 cP at room temperature. Elowever, the poor electrochemical stability of these compounds prevented them from being used in batteries. 

Since A,A -disubstituted hydrazines are readily available from a variety of sources (see Volume I, Chapter 14), their dehydrogenation constitutes a widely applicable route to both aliphatic and aromatic azo compounds. Such oxidative procedures are of particular value in the aliphatic series because so many of the procedures applicable to aromatic compounds, such as the coupling with diazonium salts, have no counterpart. The oxidation reactions permit the formation not only of azoalkanes, but also of a host of azo compounds containing other functional groups, e.g., a-carbonyl azo compounds [83], a-nitrile azo compounds [84], azo derivatives of phosphoric acid [85], phenyl-phosphoric acid derivatives [86],... 

Examples for the oxidation of nitrogen-containing compounds via halide ions as redox catalysts are listed in Table 4, No. 51-56. In this way, primary amines are transformed to nitriles using the system NaBr/MeOH (Table 4, No. 52) Thus, 1,2-diaminocyclohexane is cleaved to yield adiponitrile (Eq. (64))... 

The pyrolysis gas chromatogram of ABS at 550°C changes considerably when the pyrolysis products are passed over zeolite catalysts. The specific activity towards certain reactions, e.g., cycliza-tion, aromatization, or chain cleavage is somewhat dependent on the nature of the individual zeolite. In general, enhanced benzene, toluene, ethylbenzene at the cost of dimer, trimer formation is observed. Nitrogen containing compounds do not appear in the pyrolysis oil after catalytic conversion. However, the product gas is rich in nitriles (132). 

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