Amino group directing effect

Monosubstitution of the free amine may be achieved by using a less reactive electrophile. Thus aniline and o-toluidine may be mono-iodinated (Expt 6.60) by treatment with iodine (in the presence of sodium hydrogen carbonate or calcium carbonate to remove the liberated hydrogen iodide), the substituent entering the position para to the amino group. Direct iodination can also be effected by using the more powerfully electrophilic reagent, iodine monochloride... 

Meyer, W. P. Martin, J. C. Substituent effects of alkoxy and amino groups directly bonded to cationic carbon in the perpendicularly twisted geometry. 2-Oxa- and 2-aza-l-adamantyl tosy-lates./. Am. Chem. Soc. 1976, 98, 1231-1241. 

The Pomeranz-Fritsch-Bobbitt cyclisation of activated amino-acetal 38 yielded the desired 4-hydroxyquinoline 39 in acceptable yield. The non-obvious regioselectivity of the cyclisation can be attributed to the overriding para-directing effect of alkoxy groups. ... 

For a review of the directing and orienting effects of amino groups, see Chuchani, G. in Patai The Chemistry of the Amino Group Wiley NY, 1968, p. 250 for ether groups see Kohnstam, G. Williams, D.L.H. in Patai The Chemistry of the Ether Linkage Wiley NY, 1967, p. 132. 

Several indanes (8) were reduced to hexahydroindanes over Rh-Al203. The stereochemistry of the ring junction is established at the stage of the reduction of the tetrasubstituted double bonds. Only the amino group shows a strong directive effect.8... 

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... 

We turn now to the historical background to the effects of nitro and amino groups in aromatic systems. It would be appropriate to mention here that there have been several articles pertinent to these topics in earlier volumes of the Series. In 1968 Chuchani contributed a chapter on the directing and activating effects of the amino group and related groups32, with over 340 references. In 1970 Urbahski reviewed the directing effects of... 

In the nineteen-twenties the examination of the directing effects of nitro, amino and related groups was prominent in the work of various research groups, particularly those involved in the controversies regarding electronic theories of organic chemistry which raged from 1924 for several years44-46. Thus in 1926-27 Robert Robinson and his... 

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