Aliphatic and aromatic amines

Both aliphatic and aromatic aldehydes condense with primary amines, aliphatic and aromatic, to form N substituted imines. The purely aliphatic imines (C, to C,) can be obtained in 50 80% yield however, these compounds are unstable and should be used immediately after distillation. ... 

Side reactions which may occur during their formation have been studied. On the other hand, Schiff bases from substituted benzaldehydes and amines, aliphatic and aromatic, are more stable and have been prepared in large numbers. The benzaldehyde entity may carry a halo, hydroxyl, methoxyl, dialkylamino, or nitro group. Usually, an immediate reaction occurs upon mixing the two reactants either without a solvent or in dilute alcohol, as illustrated by the synthesis of benzalaniline, C,H,CH=NC,H, (87%). ... 

Indoor activities Cooking, tobacco smoking, use of water and solvents (amines aliphatic and aromatic hydrocarbons aldehydes halocarbons). 

N-Monosubstituted O-Alkylhydroxylamines. Various O-methylhydroxyl-amine derivatives (MeONHR) aminate aliphatic and aromatic organolithium compounds R = Me,82,83,97 n-Pr and i-Pr,83 benzyl,83,85 a-methylbenzyl,82,83,85,97... 

Urban ozone formation potential is expressed relative to ethene. It represents the potential of an organic solvents vapor to form ozone relative to fliat of efliene ((g OJg sol-vent)/(g Os/g ethene)). Several groups of solvents, including alcohols, aldehydes, amines, aliphatic and aromatic hydrocarbons, esters, ethers, and ketones are active in ozone formation. Aldehydes, xylenes, some unsaturated compounds, and some terpenes are the most active among those. 

Hofmann s amine synthesis can be applied to both aliphatic and aromatic carboxylic acid amides, benzamide, C HsCONH, thus giving aniline, C4H5NH,. 

Both aliphatic and aromatic nitro-compounds can be readily reduced in acid solution to the corresponding primary amine. Thus when a mixture of nitrobenzene and tin is treated with hydrochloric acid, the tin dissolves to give stannous chloride, SnCh, which in these circumstances then reacts with more acid to give stannic chloride, SnCl, and the nascent hydrogen produced from... 

Those reactions which are common to both aliphatic and aromatic amines and have been described under Aliphatic Amines (Section 111,123) will not be repeated in this Section except where differences in experimental technique occur. 

The melting points of the derivatives of a number of tertiary amines, both aliphatic and aromatic, are coUeoted in Table IV,100C. 

Tertiary Aliphatic and Aromatic Amines, Table IV, lOOC. 

Primary and secondary aliphatic and aromatic amines react readily with thiiranes to give 2-mercaptoethylamine derivatives (Scheme 76) (76RCR25, 66CRV297). The reaction fails or gives poor yields with amines which are sterically hindered e.g. N,iV-dicyclohexylamine) or whose nitrogen atom is weakly basic e.g. N,A/ -diphenylamine). Aromatic amines are less reactive and higher reaction temperatures are usually required for them. The reaction mechanism is Sn2 and substituted thiiranes are attacked preferentially at the least hindered... 

Low surface energy substrates, such as polyethylene or polypropylene, are generally difficult to bond with adhesives. However, cyanoacrylate-based adhesives can be effectively utilized to bond polyolefins with the use of the proper primer/activa-tor on the surface. Primer materials include tertiary aliphatic and aromatic amines, trialkyl ammonium carboxylate salts, tetraalkyl ammonium salts, phosphines, and organometallic compounds, which are initiators for alkyl cyanoacrylate polymerization [33-36]. The primer is applied as a dilute solution to the polyolefin surface, solvent is allowed to evaporate, and the specimens are assembled with a small amount of the adhesive. With the use of primers, adhesive strength can be so strong that substrate failure occurs during the course of the shear tests, as shown in Fig. 11. 

Catalytic reduction of fluormated aliphatic and aromatic nitro compounds to give oximes and amines was described previously, as was the use of dissolving metals to prepare amines [Si] Refmement of these techniques has resulted in optimized yields and, as indicated in equations 69 and 70, in selective reductions [S6, 87]... 

Selectivity and reactivity of mixed anhydrides toward primary and secondary aliphatic and aromatic amines has been studied in details [42, 43] (equation 22) Fluorocarboxyhc acids and then denvahves are used as building blocks m condensa non reactions widi dmucleophihc species for the synthesis of fluoroalkyl-subshtuted lieteroaromahc systems [S 9, 40, 44, 45, 46, 47 4S] (equations 20 21, and 23)... 

The condensation of primary amines with 2,5-dialkoxytetra-hydrofurans to give in one step N-substituted pyrroles is applicable to a variety of substituted aliphatic and aromatic amines.6 The method, largely developed by Clauson-Kaas and associates, has the advantages of simplicity, mild conditions, and generally excellent yields from readily available starting materials. 

The determination of primary amines on the macro scale is most conveniently carried out by titration in non-aqueous solution (Section 10.41), but for small quantities of amines spectroscopic methods of determination are very valuable. In some cases the procedure is applicable to aromatic amines only, and the diazotisation method described for determination of nitrite (Section 17.38) can be adapted as a method for the determination of aromatic primary amines. On the other hand, the naphthaquinone method can be applied to both aliphatic and aromatic primary amines. 

The resolution of racemic ethyl 2-chloropropionate with aliphatic and aromatic amines using Candida cylindracea lipase (CCL) [28] was one of the first examples that showed the possibilities of this kind of processes for the resolution of racemic esters or the preparation of chiral amides in benign conditions. Normally, in these enzymatic aminolysis reactions the enzyme is selective toward the (S)-isomer of the ester. Recently, the resolution ofthis ester has been carried out through a dynamic kinetic resolution (DKR) via aminolysis catalyzed by encapsulated CCL in the presence of triphenylphosphonium chloride immobilized on Merrifield resin (Scheme 7.13). This process has allowed the preparation of (S)-amides with high isolated yields and good enantiomeric excesses [29]. 

Reaction with chloroform under basic conditions is a common test for primary amines, both aliphatic and aromatic, since isocyanides have very strong bad odors. The reaction probably proceeds by an SnIcB mechanism with dichlorocarbene as an intermediate ... 

Primary aliphatic and aromatic amines [3, 14], yield fluorescent derivatives. Primary [15] aromatic amines yield stable yellow-colored derivatives that can be eluted from the TLC layer [16]. 

---