Diels-Alder reaction between naphthalene and N-phenylmaleimide under ambient and high pressure conditions

Abstract

The rate and equilibrium constants for the Diels-Alder reactions between benzene and naphthalene as dienes and tetracyanoethylene, maleic anhydride and N-phenylmaleimide as dienophiles at 25 °С were estimated from empirical rule. The highest yield of the adduct was predicted for the reaction of naphthalene with N-phenylmaleimide. The time of adduct formation in 50% yield exceeds 30 years. The use of gallium chloride as a catalyst affords the exo-adduct for seven days at room temperature. The rate ((2±0.5)•10 -6 L mol -1 s -1 ) and equilibrium constants (5±2 L mol -1 ) of this reaction were determined. Under high pressure conditions (8 kbar) reaction occurs with formation of both stereo isomers at 100 °С during 80 hours.

Lewis Acid Assisted Diels–Alder Reaction with Regio- and Stereoselectivity: Anti-1,4-Adducts with Rigid Scaffolds and Their Application in Explosives Sensing

“…Besides anthracene derivatives, D–A reactions involving other arenes like naphthalene and phenanthrene are much less studied due to the low reactivity of these arenes . Reactions from limited reports in the literature usually suffer from harsh conditions, long reaction time, and relatively low yields. , Recently, our group reported the first method for synthesis of unusual anti -1,4-adducts between bulky N -phenylmaleimides and anthracene derivatives under thermal conditions . However, limited substrate scope and relatively low yields of anti -1,4-adducts still restrict the utility of the D–A reaction in synthetic organic chemistry.…”

Diels–Alder Reactions of 9-Ferrocenyl- and 9,10-Diferrocenylanthracene: Steric Control of 9,10- versus 1,4-Cycloaddition

“…The remaining chemical shifts for 15 match closely those previously reported for the exo-N-phenylmaleimide adduct with anthracene. 11 One may rationalize the marked difference between the chemical shifts of the endo and exo N-methyls in 14 and 15 in terms of the positioning of the former in the shielding cone of the central aromatic ring.…”

“…1 H NMR (500 MHz, CDCl 3 ): δ 8.90 (1H, br, H 8 ), 7.34 (1H, d, J = 7 Hz, H 5 ), 7.28 (1H, d, J = 7 Hz, H 4 ), 7.28 (1H, t, J = 7 Hz, H 7 ), 7.20 (1H, t, J = 7 Hz, H 6 ), 7.06 (1H, t, J = 7 Hz, H 3 ), 6.93 (1H, t, J = 7 Hz, H 2 ), 6. 28 (H, br, H Synthesis of 9-Ferrocenyl-11,12-(c-1-phenylpyrrol-2,5diono)-11,12-dihydrobarrelene (11). A mixture of 1 (43 mg, 0.12 mmol) and N-phenylmaleimide (17 mg, 0.1 mmol) was heated in 1,2-dichloroethane at 50 °C for 48 h. The residue was separated by chromatography (dichloromethane) to give 11 (39 mg, 0.073 mmol, 73%) as a yellow solid, mp 218 °C.…”

“…Their isotropic temperature factors were fixed to 1.2 times the equivalent isotropic displacement parameters of the parent atom. CCDC 943477 (5), 943476 (9), 943469 (10), 943474 (11), 943470 (13), 943472 (14), 943468 (16), 943467 (17), 943471 (18), 943475 (19), 943473 (23), 943478 (24), and 943479 (25) contain supplementary X-ray crystallographic data for this paper. The CIFs are provided here as Supporting Information; these data can also be obtained free of charge from the Cambridge Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/data_request/cif.…”

Stereoelectronic Effects in Dihapto-Coordinated Complexes of TpW(NO)(PMe3) and Their Manifestation in Diels−Alder Cycloaddition of Arenes

“…Under classical reaction conditions, benzenes resist Diels−Alder cycloaddition with even the most potent dienophiles, owing to their aromatic stabilization. − Cycloaddition is typically achieved by photochemical means or extreme pressures and temperatures . For example, at 100 °C and 10−12 kbar, a cycloadduct of naphthalene and maleic anhydride can be obtained in good yield; however, such a product is thermodynamically unstable under ambient pressures .…”