Condensation Of 2-naphthylamine Research Articles

Determination of Dihydrobenzoacridinone Structures by NMR, IR, and UV Spectroscopy and Mass Spectrometry

Introduction. Synthetic benzoacridinone derivatives are critical because of their applications as luminescent materials [1], antitumor drugs [2], and antibiotics [3]. The activity of such compounds was found to depend on the location of the carbonyl in the cyclic system [4]. Therefore, the location of the carbonyl in the fi nal product from three-component condensation of 2-naphthylamine, aromatic aldehydes, and dimedone is important because 9,9-dimethylor 10,10-dimethyl dihydrobenzoacridinones can be produced. The goal of the present work was to elucidate the structures of synthesized dihydrobenzoacridinone derivatives IVa–IVf. Experimental. 2-Naphthylamine (I, 1.43g, 0.01 mol), the appropriate aromatic aldehyde (IIa–IIf, 0.01 mol), and dimedone (III, 1.4 g, 0.01 mol) were refl uxed in EtOH until crystals of IVa–IVf began to precipitate (30–60 min) and then cooled. The resulting precipitate was fi ltered off, rinsed with Et2O, and recrystallized from EtOH:C6H6 (1:1). PMR and 13C NMR spectra were recorded from DMSO-d6 solutions (2–5%) on an Avance-500 spectrometer (BrukerBiospin, operating frequency 500.13 and 125.77 MHz for 1H and 13C). Chemical shifts were determined relative to TMS internal standard. COSY-45, NOESY, HSQC, and HMBC two-dimensional correlation spectra of IVa, IVd, and IVe were recorded in order to confi rm the structures and refi ne the resonances. All experimental results were obtained and processed using Topspin 2.1 software. IR spectra were recorded from thin layers or KBr pellets on a Protege-460 FTIR spectrophotometer (Nicolet). UV spectra of EtOH solutions (1·10–4 M) were taken on a Cary-300 spectrophotometer (Varian). Mass spectra of the synthesized compounds were measured using an Agilent 6890N gas chromatograph with an Agilent 5975 Inert mass-selective detector operating in electron-impact mode (70 eV) and was tuned to maximum sensitivity for the determined compounds. An HP-5ms capillary column (30 m × 0.25 mm × 0.25 μm) was connected directly to the mass spectrometer ion source. Samples were injected as CH2Cl2 solutions. Results and Discussion. Structures of synthesized 9,9-dimethyl-12-[5-(4-nitrophenyl)furan-2-yl]-9,10-dihydrobenzo[a] acridin-11-(7H,8H,12H)-one (IVa), 9,9-dimethyl-12-[5-(4-methoxy-2-nitrophenyl)furan-2-yl]-9,10-dihydrobenzo[a]acridin11-(7H,8H,12H)-one (IVb), 9,9-dimethyl-12-[5-(4-nitrophenyl)thiophen-2-yl]-9,10-dihydrobenzo[a]acridin-11-(7H,8H,12H)one (IVc), 9,9-dimethyl-12-[5-(3-nitrophenyl)thiophen-2-yl]-9,10-dihydrobenzo[a]acridin-11-(7H,8H,12H)-one (IVd), 12-[5-(4-bromophenyl)-1-methyl-1H-pyrrol-2-yl]-9,9-dimethyl-9,10-dihydrobenzo[a]acridin-11-(7H,8H,12H)-one (IVe), and 12-[5-(2-bromophenyl)-1-methyl-1H-pyrrol-2-yl]-9,9-dimethyl-9,10-dihydrobenzo[a]acridin-11-(7H,8H,12H)-one (IVf) were elucidated using UV, IR, PMR, and 13C NMR spectroscopy and mass spectrometry. The results indicated that condensation of 2-naphthylamine (I), aromatic aldehydes IIa–IIf, and dimedone (III) produced 9,9-dimethyl-12-[5-(aryl)furan-(or thiophen,

3-Methyl-1-sulfonic acid imidazolium hydrogen sulfate-catalyzed three-component, one-pot synthesis of 13-aryl-12H-benzo[f]indeno[1,2-b]quinoline-12-one derivatives

3-Methyl-1-sulfonic acid imidazolium hydrogen sulfate, an efficient, halogen-free, and reusable Bronsted ionic liquid, catalyzed the synthesis of 13-aryl-12H-benzo[f]indeno[1,2-b]quinoline-12-one derivatives by one-pot condensation of 2-naphthylamine, aromatic aldehydes, and 2H-indene-1,3-dione under solvent-free conditions. This method has the advantages of high yields, clean reaction, simplicity, and short reaction time. The catalyst can be recycled and reused four times without significant loss of activity.

ChemInform Abstract: Condensation of 2‐Naphthylamine or N‐Benzyl‐2‐naphthylamines with Formaldehyde and Methyl 2,2‐Dimethyl‐4,6‐dioxocyclohexane‐3‐carboxylate.

ChemInform Abstract: Condensation of 2‐Naphthylamine or N‐Benzyl‐2‐naphthylamines with Formaldehyde and Methyl 2,2‐Dimethyl‐4,6‐dioxocyclohexane‐3‐carboxylate.

Condensation of 2-naphthylamine or N-benzyl-2-naphthylamines with formaldehyde and methyl 2,2-dimethyl-4,6-dioxocyclohexane-3-carboxylate

Condensation of 2-naphthylamine with formaldehyde and methyl 2,2-dimethyl-4,6-dioxocyclohexanecarboxylate afforded depending on the reaction conditions methyl 9,9-dimethyl-11-oxo-8,9,10,12-tetrahydro-7H-benzo[a]acridine-10-carboxylate or 4-alkoxymethyl-1,4-dihydro-2′,6′-dioxo-4′,4′-dimethyl-2′H,3H,6′Hspirobenzo[f]quinoline-2,1′-cyclohexyl-3′-carboxylate. The condensation of N-benzyl-2-naphthylamines with formaldehyde and methyl 2,2-dimethyl-4,6-dioxocyclohexanecarboxylate provided with the quantitative yield the corresponding methyl 4-benzyl-1,4-dihydro-2′,6′-dioxo-4′,4′-dimethyl-2′H,3H,6′H-spirobenzo[f]quinoline-2,1′-cyclohexyl-3′-carboxylates.

ChemInform Abstract: Synthesis of Methyl 9‐Mesityl‐12‐aryl‐11‐oxo‐7,8,9,10,11,12‐hexahydrobenzo [a]acridine‐10‐carboxylates.

Abstractby condensation of 2‐naphthylamine with 2‐mesityl‐4,6‐dioxocyclohexanecarboxylate and aromatic aldehydes

Synthesis of methyl 9-mesityl-12-aryl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]- acridine-10-carboxylates

By condensation of 2-naphthylamine with methyl 2-mesityl-4,6-dioxocyclohexanecarboxylate and aromatic aldehydes new acridine derivatives were synthesized. The condensation in ethanol proceeded regiospecifi cally with moderate stereoselectivity resulting in a mixture of cis- and trans-methyl 9-mesityl-12-aryl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridine-10-carboxylate (∼40: 60%).

Synthesis of methyl 12-aryl-9,9-dimethyl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridine-10-carboxylate

A three-component condensation of 2-naphthylamine, aromatic aldehydes, and methyl 2,2-dimethyl-4,6-dioxocyclohexanecarboxylate afforded methyl (cis,trans)-12-aryl-9,9-dimethyl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridine-10-carboxylates. Spectral luminescence and nonlinear optical properties of compounds obtained were investigated.

Condensation of 2-naphthylamine with aromatic aldehydes and substituted cyclohexane-1,3-diones

New 12-aryl(or hetaryl)-9-methyl(or 4-butoxyphenyl)-8,9,10,12-tetrahydro-7H-benzo[a]acridin-11-ones possessing two asymmetric carbon atoms (C9 and C12) were synthesized by condensation of 5-methyl-or 5-(4-butoxyphenyl)cyclohexane-1,3-dione with 2-naphthylamine and aromatic or heteroaromatic aldehydes. According to the 1H NMR data, the products were isolated as mixtures of diastereoisomers.

Synthesis of Benzo[a]phenanthridine Derivatives by Condensation of N-Arylmethylene-2-naphthylamines with 5-Phenyl- and 5-(p-Methoxyphenyl)-1,3-cyclohexanediones

Condensation of N-arylmethylene-2-naphthylamines with 5-phenyl- and 5-(p-methoxyphenyl)-1,3-cyclohexanediones in various solvents gave new hexahydrobenzo[a]phenanthridin-4-one derivatives. Three-component condensation of 2-naphthylamine, appropriate aldehyde, and 5-(p-methoxyphenyl)-1,3-cyclohexanedione was also studied.