Amines tetra-reacted

Complex tetra-, penta-, and hexa-bromides, together with salts containing the Sb2Br9 ion, are the products when SbBr3 and amine hydrobromides react in aqueous hydrogen bromide.733... 

Hydrolysis of (345) yields a colorless, sublimable compound (CH2)2As404 which has the adamantane structure (34. Reaction with H2S yields (347) which is insoluble in all common organic solvents, and so no structure proof has yet been possible. With methylamine or methyl-(bistrimethylsilyl)amine (345) reacts to give the 2,4,6,8-tetramethyl-2,4,6,8-tetraaza-l,3,5,7-tetra-arsaadamantane (348 R = Me) (Scheme 64) <70ZAAC(377)120>. Several other A-substituted derivatives of (348) have been described <75JOM(94)393>. 

Arylamines and hydrazines react with tosyl azide under basic conditions to yield aryl azides [1] and arenes [2], respectively, by an aza-transfer process (Scheme 5.25). Traditionally, the reaction of anilines with tosyl azides requires strong bases, such as alkyl lithiums, but acceptable yields (>50%) have been obtained under liquidiliquid phase-transfer catalytic conditions. Not surprisingly, the best yields are obtained when the aryl ring is substituted by an electron-withdrawing substituent, and the yields for the corresponding reaction with aliphatic amines are generally poor (-20%). Comparison of the catalytic effect of various quaternary ammonium salts showed that tetra-/i-butylammonium bromide produces the best conversion, but differences between the various catalysts were minimal [ 1 ]. 

The ruthenium tetroxide dioxide catalytic system is effective for the oxidation of alkanols, although it will also react with any alkene groups or amine substituents that are present. The catalyst can be used in aqueous acetonitrile containing tetra-butylammonium hydroxide with platinum electrodes in an undivided cell Primary alcohols are oxidised to the aldehyde and secondary alcohols to the ketone [30]. Anodic oxidation of ruthenium dioxide generates the tetroxide, which is the effective oxidising agent. 

Isothiocyanates can be prepared from support-bound primary amines by treatment with thiophosgene [14] or synthetic analogs thereof (Entry 5, Table 14.2). In an alternative two-step procedure, the amine is first treated with CS2 and a tertiary amine to yield an ammonium dithiocarbamate, which is subsequently desulfurized with TsCl or a chloroformate (Entry 6, Table 14.2 Experimental Procedure 14.1). Highly reactive acyl isothiocyanates have been prepared from support-bound acyl chlorides and tetra-butylammonium thiocyanate (Entry 7, Table 14.2). These acyl isothiocyanates react with amines to give the corresponding 7V-acylthiourcas, which can be used to prepare guanidines on insoluble supports (Entry 6, Table 14.3). 

Vinyl iodides are considerably more reactive than bromides in the vinylations. It may be presumed that chlorides are not generally useful, with one exception noted below, since they have not been employed in the reaction. The bromides are usually reacted with a palladium acetate-triphenyl- or tri-o-tolyl-phos-phine catalyst at about 100 C. The reaction will occur without the phosphine if a secondary amine is present. Vinyl iodides will react in the absence of a phosphine even with only a tertiary amine present.48 37 The iodides are so reactive, in fact, that reactions occur even at room temperature if potassium carbonate is the base and tetra-zi-butylammonium chloride is used as phase transfer agent in DMF solution when palladium acetate is the catalyst.88... 

Some other 3-thienyl ether derivatives have been prepared. Poly[3-oligo(oxyethylene)-4-methyltiophene] showed an absorption peak at 550 nm (95JCS(CC)2293). On the other hand, poly[3-(N-succinimido(tetra-ethoxy)oxy)-4-methylthiophene] was prepared and it is able to react with amines to give the corresponding carbamate with a 15-crown-5 attached substructure. This polymer showed absorption at 429 nm and fluorescence at 543 nm (04T11169). 

Ipaktschi and Sharifl reported the palladium-catalyzed synthesis of 2,7-diamino fluorenones by two indirect routes due to the base sensitivity of fluorenones [182]. First, 2,7-dibromofluorene was reacted with secondary amines, and subsequent oxidation of the product formed the diaminofluorenone. Alternatively, reaction of ami-nostannanes derived from secondary amines with 2,7-dibromofluorenone gave yields of the fluorenone ranging from 42 to 58%. Beletskaya has used the DPPF-ligated palladium system to conduct selective monoarylation of ethylene diamine, diethylene triamine, triethylene tetra-amines, and 2,2-dimethyl butane-1,3-diamine [183]. 

Many of the ashless anti-knocks are amines or phenols [26] and are related to liquid-phase oxidation inhibitors. They probably work by reacting with active radicals (particularly OH) to produce radicals which are inert. For instance, N-methyl aniline (NMA) CeHsNHCHs probably produces stabilized CeHsNCHs radicals which, because of their resonance stabilization, are unable to react to regenerate active radicals again and may undergo only radical recombination reactions. The rate of radical removal by this process is likely to be limited in the most favourable case by how fast the additive can react with OH to produce stabilized radicals. Although exact rates are not known, this is probably already a fast process for NMA, and unlikely to be very much faster for any other substance. Indeed, the most effective ashless anti-knock found by MacKinven [26] in an extensive study of 970 substances was a tetra-aryl hydrazine, with a molar effectiveness 2.9 times that of NMA. 

Numerous tertiary amines that also contain carboxylic acid groups form remarkably stable chelates with many metal ions. Ethylenediamine tetra-acetic acid (EDTA) can be used for determination of 40 elements by direct titration using metal-ion indicators for endpoint detection. Direct titration procedures are limited to metal ions that react rapidly with EDTA. Back titration procedures are useful for the analysis of cations that form very stable EDTA complexes and for which a satisfactory indicator is not available. EDTA is also used for determining water hardness the total concentration of calcium and magnesium expressed in terms of the calcium carbonate equivalent. 

Amine radical-cations have been generated by the treatment of para-substituted anilines with ceric ion (Stone and Waters, 1962 Fox and Waters, 1964). When the para position is free, the initial radical-cation can react further for example, the oxidation of triphenylamine with lead tetra-acetate in the presence of boron trifluoride (Allara ei al., 1965) or with iodine (Stamires and Turkevich, 1963) gives the radical cation Ph3N+ , and, when excess of triphenylamine is used, the former oxidant leads to the radical-cation of A(, .A/, W, A -tetraphenylbenzidine. The only radical observed by the oxidation of dimethylanihne either electrochemically (Mzoguchi and Adams, 1962) or with lead tetraacetate and boron trifluoride (Allara et al., 1965) is the radical-cation of iV, .A, .A7, iV -tetramethylbenzidine. The relatively stable (hindered) anilino radical (40) has been generated from the corresponding aniline by flash photolysis audits e.s.r. spectrum has been measured in n-hexane (Land and Porter, 1961). The electronic spectrum of this radical is very similar to that of the unsubstituted anilino radical, detected during flash photolysis of aniline, but this radical is so short-lived that it has not yet been detected by e.s.r. 

One of the two hydrogen atoms of phosphoramidates can be temporarily blocked with a trimethylsilyl group. The sodium salt of diethyl V-(trimethylsilyl)phosphoramidate (102) reacted with alkyl bromides in benzene in the presence of 10 mol % of tetra-n-butylammonium bromide to afford, after desilylation, the corresponding V-alkyl derivatives (103) in 79-95% yields for primary alkyl halides. Secondary alkyl halides gave poor results (Scheme 43). The addition of the quaternary ammonium salt is essential to promote the alkylation reaction. Hexamethyldisilazane and its cyclic analogs can also be utilized in the preparation of amines under moderate conditions (Scheme 43). ... 

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