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Reaction of 3-Amino-2H-azirines with 2-Amino-4,6-dinitrophenol (Picramic Acid): Synthesis of Quinazoline- and 1,3-Benzoxazole Derivatives

By Jose M Villalgordo, Beverly R Vincent and Heinz Heimgartner


The reaction of 3-(dimethylamino)-2H-azirines 1a-c and 2-amino-4,6-dinitrophenol (picramic acid, 2) in MeCN at 0° to room temperature leads to a mixture of the corresponding 1,2,3,4-tetrahydroquinazoline-2-one 5, 3-(dimethylamino)-1,2-dihydroquinazoline 6, 2-(1-aminoalkyl)-1,3-benzoxazole 7, and N-[2-(dimethylamino)phenyl]-alpha-aminocarboxamide 8 (Scheme 3). Under the same conditions, 3-(N-methyl-N-phenylamino)-2H-azirines 1d and 1e react with 2 to give exclusively the 1,3-benzoxazole derivative 7. The structure of the products has been established by X-ray crystallography. Two different reaction mechanisms for the formation of 7 are discussed in Scheme 6. Treatment of 7 with phenylisocyanate, 4-nitrobenzoylchloride, tosylchloride, and HCl leads to a derivatization of the NH2-group of 7 (Scheme 4). With NaOH or NaOMe as well as with morpholine, 7 is transformed into quinazoline derivatives 5, 14, and 15, respectively, via ring expansion (Scheme 5). In case of the reaction with morpholine, a second product 16, corresponding to structure 8, is isolated. With these results, the reaction of 1 and 2 is interpreted as the primary formation of 7, which, under the reaction conditions, reacts with Me2NH to yield the secondary products 5, 6, and 8 (Scheme 7)

Topics: Department of Chemistry, 540 Chemistry
Publisher: Wiley-Blackwell
Year: 1990
DOI identifier: 10.1002/hlca.19900730423
OAI identifier: oai:www.zora.uzh.ch:94222
Provided by: ZORA
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