Ethylene aminomethylation

C24H25NO 127927-43-9) see Saquinavir tris(trimethylsilyloxy)ethylene (CiiH2g03Si3 69097-20-7) see Saquinavir (-)-(S)-l-trityl-2-(aminomethyl)pyrrolidine (C24H26N2 98598-84-6) see Remoxipride 5 -0-trityl-2,3 -anhydro thymidine (C29H24N2O4 25442-42-6) see Zidovudine trityl chloride... 

When ammonia or primary amines are used, the product amines may participate in further aminomethylation, resulting in the formation of a mixture of amines. Other byproducts (aldehydes, alcohols, carboxamides) may also be formed. The reaction to produce tertiary amines from secondary amines, however, is fairly selective. Aminomethylation of ethylene with piperidine was reported to form /V-propyl-piperidine with 75% yield when the reaction was carried out in the presence of [Fe(CO)5] and water without an external source of CO (170°C, 14 h).207... 

Fig. 13 (a) Possible structures of hyperbranched polymer (p(X-Y)) from the conjugate addition of X (diacrylate) and Y (trifunctional amines), (b) Structures of diacrylates and trifunctional amine monomers used for the synthesis 4-(aminomethyl)piperidine) (AMP), A-methylethylenediamine (MEDA), l-(2-aminoethyl)piperazine (AEPZ), ethylene glycol diacrylate (EGDA), 1,4-butanediol diacrylate (BDDA), and 1,6-hexanediol diacrylate (HDDA). Adapted with permission from [124], Copyright 2005 Elsevier... 

Poly[thio-l-(N,N-alkyl-aminomethyl)-ethylenes] can be obtained by polymerization of N,N-dialkyl[N(thiirane-2-methyl)]amines with ZnEt2—CH3OH as initiator system... 

Most polymers belonging to this class are water-soluble only in their protonated form. As a consequence, most potentiometric titrations of these polymers have been performed with OH starting from their hydrochlorides, either in water or in mixed solvents, such as water/dioxane, water/sulfolane, water/acetonitrile 64). Many poly[thio-l-(N,N-dialkyl-aminomethyl)ethylene]s are optically active, and in these cases ORD and CD techniques may be used to study their protonation behaviour, in addition to potentiometric techniques. 

The polymers (+ )polyfthio- l-(N-sec butyl,N-methyl-aminomethyl)ethylene] and (—)poly[thio-l-(N-methyl,N-(l-phenylethyl)aminomethyl)ethylene] seem to be able to give complexes with Cu2 + in dioxane/ethanol 1 9. The nature of these complexes is not yet fully established however, an interaction between Cu2+ ions and sulphur atoms probably occurs 29). 

Partially quatemized poly[thio-l-(N-R1,N-R2-aminomethyl)ethylene]s are water-soluble. This allows to study their acid-base behaviour in water over the whole protonation range 69). 

Fig. 4. Potentiometric - - and viscosimetric -O- titration curves using HC1 as titrating reagent ( 3 = degree of protonation of residual tertiary amine groups 5 = overall degree of neutralization e = degree of neutralization of quaternary ammonium hydroxide sites) of partially quatemized poly[thio-l-(N,N-dimethyl-aminomethyl)ethylene]...

Fig. 6. Potentiometric titration cuves of dibiasic 17 (V-) 22 (A) 35 (O) and 48 ( ) and of partially quatemized poly[thio-l-N,N-dimethyl-aminomethyl)ethylene] (O) in water [titrating reagent, 1 M HC1)]. The numbers refer to the percent of quaternized nitrogens...

Vallin, D., Huguet, J., Vert, M. Acid-base and chiroptical properties of partially quatemized optically active poly[thio-l-(N,N-diethyl-aminomethyl)ethylene], in Polymeric amines and ammonium salts, (ed.) Goethals, E. J., p. 219, New York, Pergamon Press 1980... 

The diethanolamine linker 1.13 (70), obtained from aminomethyl PS resin and ethylene oxide, has been used to support boronic acids which, after SP transformations, were released with THF/H2O/ACOH 18/1/1 in 1 h at rt or, when acid-labile boronic acids were involved, with THF/H2O 9/1 in 2 h at rt. 

Benzimidazoles, benzimidazolinones and benzimidazolinethiones react with formaldehyde and secondary amines in a Mannich reaction to form AC-aminomethyl derivatives. The conversion of benzimidazoles into l-(2-hydroxyethyl) derivatives with ethylene oxide is well known. 

As has been demonstrated in Section 3.1.2.4, complexation of amino groups offers a quite different concept for reversible protection. Making use of this principle, the coordination of chromium carbyne complexes with amino acids was described as a new amino protection. Similarly, bis(ethylene-diamine)cobalt(III) complexes of amino acids constitute a new interesting method for protection which recently was extended to the development of a new type of anchoring in solid-phase synthesis (Scheme 69). First, a t-BOC amino acid is condensed with the aquabis(ethylenediamine)cobalt(lII) complex of p-aminomethylbenzoic acid. The handle obtained in this way is then linked to aminomethyl polystyrene to give the anchored amino acid (69). Due to the sufficient stability of the complex toward... 

Reaction of C5Me4(SiMe3)(SiMe2Cl) with TiCl4 results in the exclusive formation of (C5Me4SiMe2Cl)TiCl3, which is supported on (aminomethyl)polystyrene leading to the assembly of the Cp-amido compounds (Scheme 326). The supported complexes have been spectroscopically characterized and tested, in the presence of MAO, as catalysts for the polymerization of ethylene and ethylene/l-octene co-polymerizations.774... 

As modifiers, low molecular weight rubbers with carboxyl terminal reactive groups are more effective. As hardeners, we recommend phenolic Mannich bases, such as dimethylaminomethyl phenols for hot curing and ethylene di aminomethyl phenols for cold curing. 

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