Amino radicals chloride-complexed

When metal ion complexed amino radicals are produced by the reaction of A -chloro amines with reducing metal salts in the presence of alkenes, /6-halo amines are produced12-39 41. The reaction of 1-chloropiperidine with cyclohexene, iron(II) sulfate and iron(III) chloride in methanol afforded mainly the d.s-adduct of 2. The diastereoselectivity is attributed to coordination of the unprotonated amino group with the iron(III) salt, which is mainly responsible for the chlorine atom transfer. With A-chlorodimethylarnine and 4-chloromorpholine lower yields are obtained. 

The product crystallized out of the reaction mixture as the zinc chloride complex. The state of the dimethylamino radical shown in brackets in the last equation is uncertain. It may or may not be coordinated with zinc chloride or it may originate from an S 2 displacement by styryl radical on the TMT ZnCl2 complex. Curiously no dimerization or disproportionation of the 8-amino-styryl radical was observed. Perhaps the coordination by zinc chloride prevents other reactions from occurring, allowing the combination with the second amino radical to occur reasonably efficiently. The reaction works well only with conjugated alkenes. Only slight reactions were observed with olefins such as 1-octene. 

The addition reactions of the zinc chloride-complexed amino radicals, described above were carried out in the absence of 0) gen. When oxygen was bubbled through the reaction mixture, the products were not the corresponding diamines but rather amino alcohols were isolated (27). Thus with styrene and a-methylstyrene, the reaction proceeded in the following fashion. 

In complex cases, the prefixes amino- and imino- may be changed to ammonio- and iminio- and are followed by the name of the molecule representing the most complex group attached to this nitrogen atom and are preceded by the names of the other radicals attached to this nitrogen. Finally the name of the anion is added separately. For example, the name might be 1-trimethylammonio-acridine chloride or 1-acridinyltrimethylammonium chloride. 

Photolytic. Plimmer and Hummer (1969) studied the irradiation of chloramben in water (2-4 mg/L) under a 450-W mercury vapor lamp (7, >2,800 A) for 2-20 h. Chloride ion was released and a complex mixture of colored products was observed. It was postulated that amino free radicals reacted with each other via polymerization and oxidation processes. The experiment was repeated except the solution contained sodium bisulfite as an inhibitor under a nitrogen atmosphere. Oxidation did not occur and loss of the 2-chloro substituent gave 3-amino-5-chlorobenzoic acid (Plimmer and Hummer, 1969). 

Tributyltin hydride was subsequently tested in the conversion of acid chlorides to the aldehydes (Scheme 15).D6],[47] jjjg homogeneous catalyst Pd(Ph3P)4 as well as Pd(ll) complexes, such as PdCl2, can be used instead of a supported catalyst. The reaction proceeds under very mild conditions, especially compared to the Rosemnund reduction, and affords the aldehydes in very good yield. The reaction tolerates a variety of functional groups and can even convert a,/3-unsaturated acid chlorides to the a,/S-unsatu-rated aldehydes. Without the Pd the tin hydrides will reduce the acid chloride by a radical mechanism to a mixture of aldehydes and esters. With the Pd the reaction is much more rapid and selective for the aldehyde. The reaction has been applied to the synthesis of a-amino aldehydes (Scheme and a nicotinaldehyde derivatives ... 

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