Oxidative Addition of N-Aminophthalimide to Conjugated and Nonconjugated Alkylazoalkanes

Abstract

A series of g,d-unsaturated azo compounds was prepared by thermal isomerization of allylalkylhydrazones obtained from the simplest carbonyl compounds. The oxidation of N-aminophthalimide with lead tetraacetate in the presence of these unsaturated compounds gave rise to mixtures of adducts at the azo group, regioisomers of phthalimidoazimines. The oxidative addition of N-aminophthalimide to 1-isopropylazocycloalkenes afforded bicyclic C-isopropylazo-N-phthalimidoaziridines, but the same reaction with 2-alkylazopropenes did not result in any adducts with these conjugated azocompounds.

Hypervalent Iodine‐Mediated Aziridination of Alkenes: Mechanistic Insights and Requirements for Catalysis

“…Spectroscopic data were consistent with that previously reported. [11] 2-Methyl-3-(2-phenylaziridin-1-yl)quinazolin-4(3H)one (42): Yield: 84 % from styrene, 2-amino-3-methylquinazolin-1-one (26) and (diacetoxyiodo)benzene (19). Spectroscopic data were consistent with that previously reported.…”

Conversion of Bicyclic C-Azoaziridines to 2-Substituted 2H-1,2,3-triazoles

“…1 H NMR spectrum, δ, ppm (J, Hz): 1.91 (4H, m, H-5,6); 2.82 (4H, m, H-4,7); 7.28 (1H, t, J = 7.5, C 6 H 5 , H-4); 7.46 (2H, t, J = 7.5, C 6 H 5 , H-3,5); 7.99 (2H, d, J = 9, C 6 H 5 , H-2,6). 13 C NMR spectrum, δ, ppm: 21.9 (C (5,6) ); 23.1 (C (4,7) ); 118.2 (C 6 H 5 , C (2,6) ); 126.5 (C 6 H 5 , C (4) ); 129.1 (C 6 H 5 , C (3,5) ); 140.1 (C 6 H 5 , C (1) ); 145.6 (C (3a,7a) ). Mass spectrum, (7), 39 (7), 27 (4).…”

“…1 H NMR spectrum, δ, ppm (J, Hz): 1.90 (4H, m, H-5,6); 2.82 (4H, m, H-4,7); 8.13 (2H, d, J = 9.2, Ar, H-2,6); 8.30 (2H, d, J = 9.4, Ar, H-3,5). 13 C NMR spectrum, δ, ppm: 21.9 (C (5,6) ); 22.8 (C (4,7) ); 118.1 (Ar, C (2,6) ); 125.2 (Ar, C (3,5) ); 144.0 and 145.5 (Ar, C (1,4) ); 147.8 (C (3a,7a) . Analysis of samples of the reaction mixture by 1 H NMR spectroscopy after 2 days and 5 days showed that no decomposition of aziridine 1e (98 mg, 0.24 mmol) occurs.…”

“…1 H NMR spectrum, δ, ppm (J, Hz): 2.25 (2H, q, J = 6.4, H-6); 2.71 (2H, t, J = 6.2, H-7); 3.04 (2H, t, J = 6.2, H-5); 7.40 (1H, t, J = 7.3, C 6 H 5 , H-4); 7.49 (2H, t, J = 7.7, C 6 H 5 , H-3,5); 8.14 (2H, d, J = 8.1, C 6 H 5 , H-2,6). 13 C NMR spectrum, δ, ppm: 22.4 (C (6) ); 23.8 (C (7) ); 40.3 (C (5) ); 120.4 (C 6 H 5 , C (2,6) ); 129.4 (C 6 H 5 , C (4) ); 130.0 (C 6 H 5 , C (3,5) ); 140.0 (C 6 H 5 , C (1) ); 143.3 (C (7a) ); 155.6 (C (3a) ); 192.7 (C (4) Decomposition of 6-(4-Nitrophenyl)azo-7-phthalimido-7-azabicyclo[4.1.0]heptan-2-one (1g). From aziridine 1g (141 mg, 0.35 mmol), we obtained phthalimide (20 mg, 39%) and 2-(4-nitrophenyl)-2,5,6,7-tetrahydro-4H-benzo-1,2,3-triazol-4-one (3g) (38 mg, 42%), orange platelets; mp 209°C, R f 0.40 (methylene chloride).…”

“…This provides a basis for hypothesizing that oxidative addition of N-amino heterocyclic compounds to the entire series of conjugated azocycloalkenes we studied in [1][2][3][4] initially occurs at the carbon-carbon double bond to yield azoaziridines, and formation of bicyclic 1,2,3-triazoles is the result of their secondary conversions in the reaction mixture and also during isolation and purification.…”