Amines non-aromatic

A number of adducts of bis(acetylacetonato)nickel(lI) have been studied by H and 13C NMR spectroscopy.39739,407"423 In several cases, always when aromatic bases are involved, the shifts of both protons and carbons cannot be accounted for by cr- and r-delocalization mechanisms. Similar results have been found for non-aromatic amines such as piperidine derivatives, showing that in these complexes there are also alternating 13C contact shifts which have been accounted for by inclusion of spin polarization in the mechanism of electron spin transfer through the carbon skeleton with INDO-MO calculations.412... 

The fact that Nb complexes are capable of oxidatively adding the C-N bond of anilines takes the organometallic modeling a step closer to the more conventional HDN mechanisms (of e.g. quinoline). Some interesting mechanistic considerations have been put forward in this case, but more detailed studies are required in order to better understand this reaction. When other non-aromatic amines have been used as model substrates, electron-rich late metals (Ru, Ni) are better suited for cleaving C-N bonds,... 

Tetraethylammonium chloride hydrate. See Tetraethylammonium chloride Tetraethylammonium hydroxide CAS 77-98-5 EINECS/ELINCS 201-073-3 Synonyms Ethanaminium, N,N,N-triethyl-, hydroxide TEA-OH Classification Non-aromatic amines Empirical CsH2iNO Formula (C2Hs)4N OH"... 

Tetramethyl butanediamine. See N,N,N, N -Tetramethyl-1,3-butanediamine N,N,N, N -Tetramethyl-1,3-butanediamine CAS 97-84-7 EINECS/ELINCS 202-610-4 Synonyms Tetramethyl butanediamine Classification Non-aromatic amines Empirical C8H20N2... 

Classification Non-aromatic amines Specialty Chemicals Source Book-Third Edition... 

Draw all three second-order resonance structures of aniline, and explain why aromatic amines are weak bases and poor nucleophiles (as compared to non-aromatic amines). 

Table 15.9 Asymmetric reduction of imines 106 derived from non-aromatic amines catalyzed by chiral Lewis bases 116, 118, and 120-122 (Scheme 15.25 and Figures 15.5 and 15.6).

SchifT s bases A -Arylimides, Ar-N = CR2, prepared by reaction of aromatic amines with aliphatic or aromatic aldehydes and ketones. They are crystalline, weakly basic compounds which give hydrochlorides in non-aqueous solvents. With dilute aqueous acids the parent amine and carbonyl compounds are regenerated. Reduction with sodium and alcohol gives... 

The dependence of chiral recognition on the formation of the diastereomeric complex imposes constraints on the proximity of the metal binding sites, usually either an hydroxy or an amine a to a carboxyHc acid, in the analyte. Principal advantages of this technique include the abiHty to assign configuration in the absence of standards, enantioresolve non aromatic analytes, use aqueous mobile phases, acquire a stationary phase with the opposite enantioselectivity, and predict the likelihood of successful chiral resolution for a given analyte based on a weU-understood chiral recognition mechanism. 

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 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. 

Yang XB, Fu X-K, Zeng R-Q (2010) Intercalation of non-aromatic heterocyclic amines into layered zirconium glycine-N, N-dimethylphosphonate. Chem Paper 64( 1) 118-122... 

Interaction, in presence of diluent below 0°C, with isopropylamine or isobuty-lamine caused separation of explosive liquids, and with aniline, phenylhydrazine and 1,2-diphenylhydrazine, explosive solids [1], In absence of diluents, contact with most aliphatic or non-aromatic heterocyclic amines often leads to uncontrolled oxidation and/or explosions [2], During oxidation of two steroidal dienes in dry pyridine at —35 to —40°C, on one occasion each of the reactions was accompanied by violent explosions [3],... 

A new effective metal-ffee radical approach by Murphy et al generates the free radical by treatment with tetrathiafulvalene (TTF).1491 As depicted in scheme 16 the aromatic amine 79 is transformed into the diazonium salt 81 which on treatment with TTF leads to the radical 82. The following stereoselective cyclization gives the hexahydrocarba-zole scaffold 80, a substructure of alkaloids like aspi-dospermidin, strychnin and vinblastin. Also the non-toxic tris(trimethylsilyl)silane was employed for domino reactions, eg. for the preparation of the alkaloid aspidospermidin. 

The catalytic effect of quaternary ammonium salts in the basic liquid liquid two-phase alkylation of amines [1-3] is somewhat unexpected in view of the low acidity of most amines (pKfl>30). Aqueous sodium hydroxide is not a sufficiently strong base to deprotonate non-activated amines in aqueous solution and the hydroxide ion is not readily transferred into the organic phase to facilitate the homogeneous alkylation (see Chapter 1). Additionally, it is known that ion-pairs of quaternary ammonium cations with deprotonated amines are decomposed extremely rapidly by traces of water [4]. However, under solidrliquid two-phase conditions, the addition of a quaternary ammonium salt has been found to increase the rate of alkylation of non-activated amines by a factor of ca. 3-4 [5]. Similarly, the alkylation of aromatic amines is accelerated by the addition of the quaternary ammonium salt the reaction is accelerated even in the absence of an inorganic base, although under such conditions the amine is deactivated by the formation of the hydrohalide salt, and the rate of the reaction gradually decreases. Hence, the addition of even a weak base, such as... 

The greater acidities of the heteroaromatic azoles (pKa ca. 15), compared with simple acyclic and non-aromatic cyclic amines, is reflected in the ease with which the systems are /V-alkylated and /V-acylated. 

The polymerization of phenols or aromatic amines is applied in resin manufacture and the removal of phenols from waste water. Polymers produced by HRP-catalyzed coupling of phenols in non-aqueous media are potential substitutes for phenol-formaldehyde resins [123,124], and the polymerized aromatic amines find applications as conductive polymers [112]. Phenols and their resins are pollutants in aqueous effluents derived from coal conversion, paper-making, production of semiconductor chips, and the manufacture of resins and plastics. Their transformation by peroxidase and hydrogen peroxide constitutes a convenient, mild and environmentally acceptable detoxification process [125-127]. 

Pyridine is a base (pATa pyridinium cation 5.2), but it is a considerably weaker base than a typical non-aromatic heterocyclic amine such as piperidine (pATa piperidinium cation 11.2). This is because the lone pair electrons in pyridine are held in an sp orbital. The increased character of this orbital, compared with the sp orbital in piperidine, means... 

Since autoxidations of phenols and aromatic amines are non-chain radical processes, they require some rapid radical-generating step. In a few systems—e.g., hydroquinone autoxidation, this is supplied by a direct redox reaction with oxygen (11). 

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