Amines complex formation

In the presence of the radical substitution promoter [Fe2(CO)4()u,-SR)i(PPh3)2], tertiary amines react with transition metal carbonyl clusters under exceptionally mild conditions. Modified allenyl and allylic clusters similar to those described earlier have been isolated from such reactions. Two distinct types of products have been isolated (i) those involving the elimination of an alkyl group and (ii) those involving C-C coupling reactions. The product formation described in Scheme 31 was preceded by amine coordination, C-H activation, C-N cleavage, carbene-amine complex formation, transamination, and C-C coupling (6Ia.h)- Such processes are of interest in the area of hydrodenitrification (6/c). 

It can be seen that yields of azo compounds produced from p-toluidine and p-anisidine are almost quantitative, whereas yields of azo compounds from o-toluidine and c -anisidine are poor. Kinoshita rationalized this difference on the basis of steric hindrance to copper amine complex formation exerted by the ortho substituents. It is of interest to note that the yield of azo compounds obtained in the free radical initiated autoxidation of aromatic amines are not significantly affected by the position of substituent groups on the aromatic ring [175,176]. 

Jansen K, Buschmann H-J, Wego A, Dopp D, Mayer C, Drexler H-J, Holdt H-J, Schollmeyer E. Cucurbit[5]uril, decamethylcucurbit[5]uril and cucurbit[6]uril. Synthesis, solubiUty and amine complex formation. J Indus Phenom Macro Chem 2001 39 357-63. 

Ammine and Amine Complexes. Formation of the phosphate complex, [Cr(NH3)5(H2P04)] , from the reaction of [Cr(NH3)50H] ion with phosphate (pH 1-2) proceeds via parallel ion pair and ion dipole interchange pathways (Scheme 8). From kinetic studies at / = 1.0 mol dm" [LiC104], the... 

Based on the above-mentioned stereochemistry of the allylation reactions, nucleophiles have been classified into Nu (overall retention group) and Nu (overall inversion group) by the following experiments with the cyclic exo- and ent/n-acetales 12 and 13[25], No Pd-catalyzed reaction takes place with the exo-allylic acetate 12, because attack of Pd(0) from the rear side to form Tr-allyl-palladium is sterically difficult. On the other hand, smooth 7r-allylpalladium complex formation should take place with the endo-sWyWc acetate 13. The Nu -type nucleophiles must attack the 7r-allylic ligand from the endo side 14, namely tram to the exo-oriented Pd, but this is difficult. On the other hand, the attack of the Nu -type nucleophiles is directed to the Pd. and subsequent reductive elimination affords the exo products 15. Thus the allylation reaction of 13 takes place with the Nu nucleophiles (PhZnCl, formate, indenide anion) and no reaction with Nu nucleophiles (malonate. secondary amines, LiP(S)Ph2, cyclopentadienide anion). 

Allylic amine is a less reactive leaving group[7], but the allylic ammonium salts 214 (quaternary ammonium salts) can be used for allylalion(l30,131]. Allylic sulfonium salts are also used for the allylation[130]. The allylic nitrile in the cyclic aminonitrile 215 can be displaced probably via x-allylic complex formation. The possibility of the formation of the dihydropyridinium salts 216 and subsequent conjugate addition are less likelyfl 32],... 

Most reactions involve reactants and products that are dispersed in a solvent. If the amount of solvent is changed, either by diluting or concentrating the solution, the concentrations of ah reactants and products either decrease or increase. The effect of these changes in concentration is not as intuitively obvious as when the concentration of a single reactant or product is changed. As an example, let s consider how dilution affects the equilibrium position for the formation of the aqueous silver-amine complex (reaction 6.28). The equilibrium constant for this reaction is... 

Hydantoin itself can be detected ia small concentrations ia the presence of other NH-containing compounds by paper chromatography followed by detection with a mercury acetate—diphenylcarba2one spray reagent. A variety of analytical reactions has been developed for 5,5-disubstituted hydantoias, due to their medicinal iaterest. These reactions are best exemplified by reference to the assays used for 5,5-diphenylhydantoiQ (73—78), most of which are based on their cycHc ureide stmcture. Identity tests iaclude the foUowiag (/) the Zwikker reaction, consisting of the formation of a colored complex on treatment with cobalt(II) salts ia the presence of an amine (2) formation of colored copper complexes and (3) precipitation on addition of silver(I) species, due to formation of iasoluble salts at N. ... 

Monsanto has disclosed the use of carbon dioxide—amine complexes which are dehydrated, at low temperatures, with phosphoryl chloride [10025-87-3] or thionyl chloride [7719-09-7] as a viable route to a variety of aUphatic isocyanates. The process rehes on the facile formation of the intermediate salt (30).REPLACEVariations of this process, in which phosgene is used as a dehydrating agent, have been reported earlier (84). Table 2 Hsts commercially available aUphatic isocyanates. 

Polymerization Mechanism. The mechanism that accounts for the experimental observations of oxidative coupling of 2,6-disubstituted phenols involves an initial formation of aryloxy radicals from oxidation of the phenol with the oxidized form of the copper—amine complex or other catalytic agent. The aryloxy radicals couple to form cyclohexadienones, which undergo enolization and redistribution steps (32). The initial steps of the polymerization scheme for 2,6-dimethylphenol are as in equation 6. 

To minimize the formation of fuhninating silver, these complexes should not be prepared from strongly basic suspensions of silver oxide. Highly explosive fuhninating silver, beheved to consist of either silver nitride or silver imide, may detonate spontaneously when silver oxide is heated with ammonia or when alkaline solutions of a silver—amine complex are stored. Addition of appropriate amounts of HCl to a solution of fuhninating silver renders it harmless. Stable silver complexes are also formed from many ahphatic and aromatic amines, eg, ethylamine, aniline, and pyridine. 

The addition product, C QHgNa, called naphthalenesodium or sodium naphthalene complex, may be regarded as a resonance hybrid. The ether is more than just a solvent that promotes the reaction. StabiUty of the complex depends on the presence of the ether, and sodium can be Hberated by evaporating the ether or by dilution using an indifferent solvent, such as ethyl ether. A number of ether-type solvents are effective in complex preparation, such as methyl ethyl ether, ethylene glycol dimethyl ether, dioxane, and THF. Trimethyl amine also promotes complex formation. This reaction proceeds with all alkah metals. Other aromatic compounds, eg, diphenyl, anthracene, and phenanthrene, also form sodium complexes (16,20). 

CF3C0)20, 18-crown-6, Et3N, 95% yield. Complex formation of a primary amine with 18-crown-6 allows selective acylation of a secondary amine. 

The reaction has been applied to more complex enamines 13) and to dienamines 19). The reduction may be rationalized by initial protonation at the enamine carbon and subsequent decarboxylation of formate ion and addition of the hydride ion to the iminium cation. This mechanism has been given support by the reaction of the enamine (205) with deuterated formic acid 143) to give the corresponding amines. The formation of 206 on reaction with DCOOH clearly indicates that protonation at the enamine carbon is the initial step. 

Mino and Kaizerman [12] established that certain. ceric salts such as the nitrate and sulphate form very effective redox systems in the presence of organic reducing agents such as alcohols, thiols, glycols, aldehyde, and amines. Duke and coworkers [14,15] suggested the formation of an intermediate complex between the substrate and ceric ion, which subsequently is disproportionate to a free radical species. Evidence of complex formation between Ce(IV) and cellulose has been studied by several investigators [16-19]. Using alcohol the reaction can be written as follows ... 

A similarly undesirable situation is brought about in unduly alkaline solutions caused by the indiscriminate use of amines which may lead to high dissolution rates of copper from its alloys owing to complex formation. The standards discussed in Section 5.5 are aimed at avoiding these undesirable situations. 

As a result the research emphasis in this field focused on efforts to design experiments in which it might be possible to determine to which one of the foregoing three rate equations the observed second-order rate coefficient actually corresponded. More specifically, the objective was to observe one and the same system first under conditions in which complex decomposition (fcp) was rate-determining and then under conditions in which complex formation (kF) was ratedetermining. A system in which either formation or decomposition was subject to some form of catalysis was thus indicated. In displacements with primary and secondary amines the transformation of reactants to products necessarily involves the transfer of a proton at some stage of the reaction. Such reactions are potential-... 

The resulting water helps to extend the life of the dry cell by providing moisture for the movement of the ionic species. A second reaction, that extends the usefulness of this cell, is the formation of an amine complex of zinc ions in the cell ... 

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