Imino groups, bridging

The reaction between Ni(cod)2 and iminobenzophenone has been carried out as outlined in equation (33).192 The bis-imino complex (36) is trinuclear in the solid state containing bridging, terminal, end-on and side-on coordinated imino groups. 

The structure of inosose bis(phenylhydrazones) resembles that of saccharide osazones in that the bishydrazone residues in both are chelated that is, bridged by an imino group (the other NH group is unchelated). 

In the synthesis of commercial sulfur-heterocycles two interesting reactions are used (i) diphenylamines may be connected by a sulfur bridge in the orfho-positions (ii) the amino grouping of sulfonamides undergoes condensation reactions with neighboring imino- and amide groups. 

Selecting a sulphonated dye molecule containing an amino group as the nucleophile leads directly to a dichlorotriazine dye. In certain cases a suitable intermediate may be condensed with cyanuric chloride and then the chromogenic grouping is synthesised from this reaction product. Both of these routes are illustrated in a simple way for Cl Reactive Red 1 (7.1) in Scheme 7.7. In these dyes the electronic effects responsible for the lability of the chloro substituents are muted by feedback of electrons from the electron-donating imino bridging... 

The benzyne route to 1-cyanobenzocyclobutenes has been employed for the synthesis of a myriad of complex natural products. The cyano group in (74) was used to attach the dienophile as well as for building die imino bridge of (75), an important precursor for some diterpene alkaloids (Scheme 15).110... 

V-aminated end-imino (imino-bridged) compounds like 392 (86JHC1331). These products result from the addition of the reagent to the keto group without dehydration, followed by regiospecific cyclization of the secondary amino function into the vinylene group. 

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