Tris amine, formation

Markus Albrecht and co-workers synthesised three M4L4 tetrahedra based on different C3-symmetric imine type ligands. The ligands are shown in Fig. 16. For the formation of these ligands, 2,3-dihydroxybenzaldehyde was reacted with the product of the reduction of the corresponding trinitro derivative (L21) or with a tris-amine derivative (L22, L23) [30, 135-141]. 

In 2002, Ley reported the application of resin-bound reagents and polymers towards the synthesis of carpanone [57]. In the final steps towards carpanone, a resin-bound Co(salen) catalyst was used to give the desired intermediate along with the formation of a small amount of aldehyde by-product. To remove this byproduct, a resin-bound tris-amine scavenger was used, yielding the desired product in high purity (Scheme 8.42). 

An important mode of oxidation for -phenylenediamines is the formation of ben2oquinonediimines, easily obtained by oxidation with silver oxide in ether solution (17). DHmines undergo 1,4 additions with amines to generate tri- and tetraamines which readily oxidi2e in air to highly conjugated, colored products. An example of this is the formation of Bandrowski s base [20048-27-5] when -phenylenediamine is oxidi2ed with potassium ferricyanide (18). 

Tris(2-aminoethyl)amine, CH2CI2. This amine acts as the deblocking agent and the scavenger for the dibenzofulvene and does not cause the formation of precipitates or emulsions, which sometimes occur. ... 

Diethyl methylphosphonite in refluxing dialkylamine is the favored method for the formation of 37/-azepines from nitroarenes,75,176,207 although tributylphosphane and tri-piperidinophosphane are recommended for the deoxygenation of nitrobenzene in piperidine.79 Deoxygenation of nitrobenzene in diethylamine furnishes Ar,Ar-diethyl-3/f-azepin-2-amine, and a range of 5-substituted 3//-azepines 97 have been prepared in a similar manner from 4-sub-stituted nitroarenes.79,176 Curiously, the corresponding 2-substituted nitroarenes, with the exception of 2-nitrotoluene, yield only tarry products. 

The reaction of 1,2-dithiolanes with 2- and 4-picolyllithium has been examined <96PS(112)101> and the reactions of thioanhydrides such as 94 with both thiols <95JOC3964> and amines <96TL5337> have been reported. Treatment of 1,2-dithiolium salts with lithium or thallium cyclopentadienide results in formation of a variety of bi-, tri- and tetracyclic products <96LA109>. Reaction of 95 with trimethyl phosphite gives some of the desired coupling product but also the phosphonates 96 <96PS(109)557>. 

An alternative method of synthesis of N3P3Cl6 has been developed recently, based on the reaction of tris (trimethylsilyl) amine and phosphorus pentachloride (40). This reaction either preferentially leads to the formation of N3P3C16 or to an N-silylated phosphoranimine intermediate C13P - NSiMe3, depending on the reaction conditions used. Thus the reaction between tris (trimethylsilylamine) and PC15 in methylene chloride at 40° C affords a mixture of cyclo and linear phosphazenes, which has been shown by an NMR analysis to contain up to 76% of N3P3C16 (Eq. 2). 

The choice of tridentate amine has a critical impact on the coordination mode of the ambidentate nitrite ligand, N02.499,500 Complexes with substituted tri- and tetraamines have shown that bulky substituents may prevent the formation of the -N02 bridged polymeric complexes, and the intramolecular hydrogen network may stabilize N coordination of nitrite. 

Bulk electrochemical reduction of the platinum(IV) complex of the tridentate ligand l,l,l-tris(aminomethyl)ethane(tame), [Pt(tame)2]4+, leads to the quantitative formation of [Pt(tame)2]2+ (28), in which one of the amine donor groups in tame remains noncoordinated.141 The X-ray structure of the diprotonated complex [Pt(Htame)2]4+, as its tetrachlorozincate(II) salt, is also reported. 

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