ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 1, pp. 131–132. © Pleiades Publishing, Ltd., 2016. Original Russian Text © N.I. Omelichkin, L.G. Minyaeva, V.V. Mezheritskii, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 1, pp. 137–138.

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Acylation of 1H-1,2-Diazaphenalenes with Aliphatic Carboxylic Acid Anhydrides N. I. Omelichkin, L. G. Minyaeva, and V. V. Mezheritskii† Research Institute of Physical and Organic Chemistry, Southern Federal University, pr. Stachki 194/2, Rostov-on-Don, 344090, Russia e-mail: [email protected] Received May 18, 2015

DOI: 10.1134/S1070428016010255 As shown in [1], diazaphenalenes are acylated at the pyrrole-type nitrogen atom on heating in acetic anhydride for 30 min in the presence of a catalytic amount of perchloric acid. We have found that this reaction is also possible in the absence of a catalyst on heating in aliphatic carboxylic acid anhydride for a short time. Heating of 6-methoxy-3-methyl-1H-1,2diazaphenalene (1) in acetic anhydride for 5 min afforded 87% of compound 3a which was identified by spectral data as 1-acetyl-6-methoxy-3-methyl-1H-1,2diazaphenalene [1]. Likewise, compound 3b was obtained in 70% yield by heating diazaphenalene 1 in propionic anhydride for 3‒5 min; heating of the reaction mixture for a longer time resulted in tarring. 1H-1,2-Diazaphenalenes of the acenaphthene series (aceperidazines) were readily acylated as well. By reactions of 3-methylaceperidazine 2 with acetic and propionic anhydrides on heating under reflux for 3– 5 min we obtained 1-acyl derivatives 4a and 4b, respectively (Scheme 1). The yields of 4a and 4b decreased when the reaction time increased.

We have optimized the procedure for the synthesis of initial 3-methylaceperidazine 2. Chromatographically pure compound 2 was isolated in more than 90% yield when 5-acetyl-6-hydroxyacenaphthene (5) was heated in boiling hydrazine hydrate for a short time (Scheme 2); according to [2], the yield of 2 was only 51%. The melting point and spectral parameters of the product were identical to those of compound 2 described in [2]. Scheme 2. OH

5

HN

R3

N

N

Me

(R3CO)2O

R1

R2 1, 2

N

Me

2

1-(6-Methoxy-3-methyl-1H-1,2-diazaphenalen-1yl)ethanone (3a). A suspension of 54 mg (0.25 mmol) of 6-methoxy-3-methyl-1H-1,2-diazaphenalene (1) in 1 mL of acetic anhydride was heated until the mixture became homogeneous, heated for 3‒5 min under reflux, and cooled. The precipitate was filtered off and purified by column chromatography on aluminum oxide using chloroform as eluent. Yield 55 mg (82%),

R1 R2 3a, 3b, 4a, 4b

1, 3, R1 = H, R2 = MeO; 2, 4, R1R2 = CH2CH2; R3 = Me (a), Et (b). †

HN

3-Methyl-6,7-dihydro-1H-indeno[6,7,1-def]cinnoline (2). A suspension of 424 mg (2 mmol) of 1-(6-hydroxyacenaphthen-5-yl)ethanone (5) in 5 mL of hydrazine hydrate was heated for 5 min under reflux. The mixture was cooled, and the precipitate was filtered off and washed with aqueous ethanol. Yield 398 mg (96%), yellow solid, mp 189‒194°C; published data [2]: mp 191‒192°C.

O Me

Me N 2H 4 · H 2O

Scheme 1. N

O

Deceased.

131

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colorless solid, mp 165‒166°C (from EtOH); published data [1]: mp 166°C. Compounds 3b, 4a, and 4b were synthesized in a similar way. 1-(6-Methoxy-3-methyl-1H-1,2-diazaphenalen-1yl)propan-1-one (3b). Yield 70%, colorless solid, mp 165‒167°C (from EtOH). IR spectrum, ν, cm–1: 1677 (C=O), 1637 (C=N). 1H NMR spectrum (CDCl3), δ, ppm: 1.23 t (3H, CH3CH2, 3J = 7.4 Hz), 2.30 s (3H, 3-CH3), 2.97 q (2H, CH3CH2, 3J = 7.4 Hz), 3.99 s (3H, OCH3), 6.75 d (1H, 4-H, J4, 5 = 8.05 Hz), 7.13 d (1H, 5-H, J5, 4 = 8.37 Hz), 7.42 t (1H, 8-H), 7.74 d.d (1H, 9-H, 3J 9, 8 = 8.21, 4J 9, 7 = 0.8 Hz), 8.73 d.d (1H, 7-H, 3J7,8 = 8.21, 4J7,9 = 0.8 Hz). Mass spectrum: m/z 268 [M]+. 1-(3-Methyl-6,7-dihydro-1H-indeno[6,7,1-def]cinnolin-1-yl)ethanone (4a). Yield 88%, yellow– green solid, mp 171‒173.5°C. IR spectrum, ν, cm–1: 1680 (C=O), 1624 (C=N). 1H NMR spectrum (CDCl3), δ, ppm: 2.26 s (3H, CH 3 CO), 2.51 s (3H, 3-CH 3 ), 3.30 s (4H, CH2CH2), 6.98 d (1H, 4-H, J4, 5 = 7.09 Hz), 7.08 d (1H, 5-H, J5, 4 = 7.09 Hz). 7.15 d (1H, 8-H, J8,9 = 7.89 Hz), 7.44 d (1H, 9-H, J9,8 = 7.89 Hz). Mass spectrum: m/z 250 [M]+. 1-(3-Methyl-6,7-dihydro-1H-indeno[6,7,1-def]cinnolin-1-yl)propan-1-one (4b). Yield 81%, brown solid, mp 173‒177°C. IR spectrum, ν, cm –1 : 1681 (C=O), 1625 (C=N). 1H NMR spectrum (CDCl3), δ, ppm: 1.22 t (3H, CH3CH2, 3J = 7.4 Hz), 2.26 s (3H,

CH3), 2.92 q (2H, CH3CH2, 3J = 7.4 Hz), 3.31 s (4H, CH2CH2), 7.00 d (1H, 4-H, J4, 5 = 7.37 Hz), 7.09 d (1H, 5-H, J5,4 = 7.01 Hz), 7.17 d (1H, 8-H, J8,9 = 8.07 Hz), 8.50 d (1H, 9-H, J9, 8 = 8.07 Hz). Mass spectrum: m/z 264 [M]+. The 1 H NMR spectra were recorded on Varian Unity-300 (300 MHz) and Bruker DPX-250 spectrometers (250 MHz) (Educational Research Laboratory of Resonance Spectroscopy, Chemistry of Natural and High Molecular Weight Compounds Department, Southern Federal University) using tetramethylsilane as internal standard. The IR spectra were measured on a Varian Excalibur 3100 FT-IR spectrometer equipped with an ATR accessory. The mass spectra (electron impact, 70 eV) were obtained on a Shimadzu GCMSQP2010 SE instrument with direct sample admission into the ion source. This study was performed under financial support by the Ministry of Education and Sciences of the Russian Federation in the framework of a state assignment (project no. 1895). REFERENCES 1. Elisevich, D.M., Mezheritskii, V.V., and Dorofeenko, G.N., Zh. Org. Khim., 1981, vol. 17, p. 1751. 2. Mezheritskii, V.V., Minyaeva, L.G., Golyanskaya, O.M., Tyurin, R.V., Borbulevich, O.Ya., Borodkin, G.S., and Antonov, A.N., Russ. J. Org. Chem., 2006, vol. 42, p. 278.

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