Synthesis and Structure of Derivatives of 9‐(2‐Oxopropyl)‐1,5‐dinitro‐7,8‐benzo‐3‐azabicyclo [3.3.1]non‐7‐en‐6‐ones.

Abstract

Synthesis and Structure of Derivatives of 9-(2-Oxopropyl)-1,5-dinitro-7,8-benzo--3-azabicyclo[3.3.1]non-7-en-6-ones. -Mannich reaction of the Yanovsky adduct (III) of 2,4-dinitronaphthol provides the title compounds (VI), which are new compounds interesting both as synthons for organic synthesis and as potential biologically active compounds. Their structure and conformation are established by molecular spectroscopy and X-ray diffraction analysis. -(YAKUNINA, I. E.; SHAKHKELDYAN, I. V.; ATROSHENKO, Y. M.; BORBULEVICH, O. Y.; NESTEROV, V. V.; KOPYSHEV, M. B.; TROITSKII, N. A.; EFREMOV, Y. A.; ALIFANOVA, E. N.; SUBBOTIN, V. A.; Russ.

Nitro-Mannich Reaction

“…The same group also demonstrated that similar reactions could be performed using Grignard reagents in place of NaBH 4 . This methodology has since been extended to a variety of other m -dinitroaromatic, dinitrobicycloaromatic, and dinitroheteroaromatic rings. − …”

Nucleophilic Dearomatizing (DNAr) Reactions of Aromatic C,H-Systems. A Mature Paradigm in Organic Synthesis

“…Similar to the phenolate series, bis-ABN 562 was formed when 1,4-butanediamine was used in the Mannich condensation. On the basis of NMR studies and semiempirical calculations, it was concluded that the piperidine ring of 561a (R 3 = Me) adopts predominantly a chair conformation with the N -methyl and oxopropyl groups occupying equatorial positions 81 37 Conjugate Addition of Stabilized Cabanions to 9-Nitroanthracene 461 entryR 1 E + yield (%) 1 CH( n -Pr)COCH 3 HCl 499c (37) a 2 CMe 2 COCH 3 HCl 499d (43) a 3 CMe 2 NO 2 HCl 499e (76) b 4 CH(CO 2 Et) 2 HCl 499f (68) b 5 CMe(CO 2 Et) 2 HCl 499g (75) b 6 CH(CN) 2 HCl 499h (70) b 7 CH 2 COCH 3 MeI 567a (40) c 8 CH 2 COPh MeI 567b (18) c 9 CHMeCOCH 3 MeI 567c (18) c 10 CH( n -Pr)COCH 3 MeI 567d (3) c 11 CH(Bn)COCH 3 MeI 567e (8) c 12 2-oxocyclohexyl MeI 567f (42) c 13 CMe 2 COCH 3 MeI 567g (6) c 14 CMe 2 NO 2 PhCH 2 Cl 567i (59) b 15 CH(CO 2 Et) 2 PhCH 2 Cl 567j (63) b 16 CMe(CO 2 Et) 2 PhCH 2 Br 567k (69) b a Data taken from ref .…”

“…On the basis of NMR studies and semiempirical calculations, it was concluded that the piperidine ring of 561a (R 3 ) Me) adopts predominantly a chair conformation with the N-methyl and oxopropyl groups occupying equatorial positions. 293 Metalated ketones were also shown to form σ-complexes 563 with 9-nitroanthracene 461. 294 Oxidation of the adducts proceeding from acetone, acetophenone, butanone, and methyl 1-naphthyl ketone with hydrogen peroxide gave 9-nitroanthracenes alkylated in position 10, 564a-c,h.…”

Hydride adducts of dinitroquinolines in multicomponent Mannich reaction

“…We formerly developed the preparation method of 3-azabicyclo[3.3.1]nonanes proceeding from aromatic dinitro compounds [4]. In this study we examined Mannich condensation of hydride adducts of dinitroderivatives of 8-oxyquinoline, 8-oxyquinaldine, and 3,4-dihydroquinolin-2-one aiming at the preparation of 3-azabicyclo[3.3.1]nonanes fused with a pyridine ring.…”