Secondary aromatic amines ring opening

The amount of catalyst (scandium trisdodecyl sulfate) and ligand, (14), in the ring opening of czT-1,2-disubstituted oxiranes with primary and secondary aromatic amines in water were varied to maximize the yields.33 In all but two cases, the reaction, under ideal conditions, yielded the j3-amino alcohols in >81% yield with enantioselectivity ... 

Pyridine (and quinoline) which in so many respects are aromatic and comparable to benzene, lose this character completely on hydrogenation to piperidine (and hydroquinoline), which are entirely of the same nature as secondary aliphatic amines. The completely hydrogenated heterocyclic bases undergo degradation reactions which have become important particularly in the investigation of the constitution of alkaloids. A. W. Hofmann s method of opening rings by means of exhaustive methylation may be illustrated with piperidine. By thermal decomposition of the quaternary ammonium base a C—N-link-age is broken and at the same time water is eliminated. 

Many authors elucidated functionalization of polymers containing reactive oxirane moieties. Epoxidized NR, BR, IR and/or the respective model hydrocarbons, poly (butadiene-co-isoprene, various epoxy resins, poly (2,3-epoxypro-pyl methacrylate) and its copolymers or grafted systems were mostly exploited. Stabilizers based on epoxidized unsaturated rubbers are of the top interest. The mechanism of the functionalization process was studied in details by means of 3,4-epoxy-4-methylheptane and 1,2-epoxy-3-ethyl-2-methylpentane as model compounds [289]. The ring opening of the asymmetric oxirane is regiospecific. Aliphatic primary amines attack the least substituted carbon atom and can be involved in crosslink formation. Aromatic primary and secondary amines are less reactive than aliphatic ones because of their lower basicity the attack on the least substituted carbon atom is however preferred too. 

With R4 = CH(Et)CH2OH ring opening occurs to give a dihydrooxazole (see Section 1.4.6.2.1.2.).54 d As with secondary aliphatic amines (see footnote b), the 3-sulfanyl compounds also react with aromatic amines to yield the corresponding 3-anilinobenzo[e]-l,4,2-dithiazines (see also refs 63 and 64). 

This methodology has also been employed for the preparation of tetradentate ligands by exchanging the primary amines for C2-symmetric primary diamines (eq 4). For example, from (/ ,/ -1,2-diamino-1,2-diphenylethane, diastereomeric ligand B was obtained in 84% yield. These aromatic amines are sufficiently reactive to open the aziridine ring. Due to steric hindrance, no further reaction of the secondary amine moieties with (5)-A -trifluoromethylsulfonyl-2-isopropylaziridine was observed. This tetradentate ligand was inferior to his(sulfonamides) as catalyst... 

Secondary amines are also the products of the deamination of 1,1-disubstituted aromatic hydrazines, and the ring-opening and recyclization of iV-alkyl-2-benzylpyridinium salts to form 2-alkylaminobiphenyls. ... 

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