Quinazoline derivatives exhibit a wide range of biological activities, finding use as anticancer, antibacterial, antimalarial and antiviral agents. Quinazoline derivatives are widely used as α1-adrenoreceptor blockers and as well in recent years quinazolines based OLED materials have gained high attention. Several methods for the modification of quinazolines 4th position are known, yet the modification of the 2nd position still poses a challenge. In this work the sulfonyl group dance was used to obtain 4-azido-2-sulfonylquinazolines, which inverse quinazolines regioselectivity in SNAr reactions, selectively substituting the 2nd position with cyclic secondary amines, resulting in 2-amino-4-azidoquinazolines. The regioselectivity of the transformation was proven by chemical synthesis, NMR and X-ray structure analysis. Further more we show the use of the products for the synthesis of phosphoronylidene- and fluorescent 4-triazolylquinazolines, as well we develop a novel synthesis pathway towards α1-adrenoreceptor blockers terazosin and prazosin.