Unusual Stabilization of 1,2-Diamino Derivatives of Quincorine and Quincoridine by Carbon Dioxide: Persistent Crystalline prim-Ammonium-Carbamate Salts and Their Reactivity towards Isatoic Acid Anhydride

• Published in: European journal of organic chemistry Vol. 2003; no. 19; pp. 3784 - 3790
• Main Authors: Neda, Ion, Kaukorat, Thomas, Fischer, Axel K.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.10.2003; WILEY‐VCH Verlag; Wiley
• Subjects: Amino alcohols; Carboxylation; Chemistry; Chemistry, Organic; Nitrogen heterocycles; Physical Sciences; Science & Technology; ENANTIOPURE; CINCHONA ALKALOIDS; nitrogen heterocycles; carboxylation; KEY DERIVATIVES; 10,11-DIDEHYDRO; amino alcohols
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.200300211

The reaction of N‐methylisatoic anhydride 1 with a series of quincorine (QCI) and quincoridine (QCD) derivatives furnished the corresponding QCI‐ and QCD‐substituted anthranilic acid amides 4−9. In the synthesis of 4−9, we investigated the influence of the C5 substituent of 2‐aminomethyl derivatives of QCI and QCD on their basicity and polarity and, therefore, on their reactivity towards isatoic acid anhydride. By exposing a number of 2‐aminomethyl derivatives of QCI and QCD to (carbon dioxide from) air, the formation of carbon dioxide adducts 10−15 was observed. In an unusual reaction, we obtained the first set of chiral ammonium carbamates derived from primary amines, which provides a convenient method for purifying and stabilizing aminomethyl derivatives of QCI and QCD. All compounds were fully characterized by spectroscopic methods. In addition, the structure of 11 was proved by X‐ray crystal structure determination. The heterocyclic nitrogen atoms display trigonal‐pyramidal coordination geometries; the amido group is essentially planar. N‐2′ of the ammonium ion is a triple hydrogen bond donor to the carboxylato oxygen atoms of three different carbamate anions. The resulting net effect is a hydrophilic plane parallel to the ab plane. The crystal packing involves six classical hydrogen bonds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)