Synthesis and Structure of 7H-12-Oxa-3,7-diazapleiadenes

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1 ISS , Russian Journal of rganic Chemistry, 2011, Vol. 47, o. 9, pp Pleiades Publishing, Ltd., riginal Russian Text V.V. Tkachev, G.V. Shilov, S.M. Aldoshin, Yu.A. Sayapin, Duong ghia Bang, V.. Komissarov, V.I. Minkin, 2011, published in Zhurnal rganicheskoi Khimii, 2011, Vol. 47, o. 9, pp Synthesis and Structure of 7H-12-xa-3,7-diazapleiadenes V. V. Tkachev a, G. V. Shilov a, S. M. Aldoshin a, Yu. A. Sayapin b, c, Duong ghia Bang b, V.. Komissarov b, and V. I. Minkin b, c a Institute of Chemical Physics Problems, Russian Academy of Sciences, pr. Akademika.. Semenova 1, Chernogolovka, Moscow oblast, Russia sma@icp.ac.ru b Institute of Physical and rganic Chemistry, Southern Federal University, pr. Stachki 194/2, Rostov-on-Don, Russia c Southern Research Center, Russian Academy of Sciences, Rostov-on-Don, Russia Received January 27, 2011 Abstract The molecular structures of 9,11-di-tert-butyl-2,4-dimethyl-7H-12-oxa-3,7-diazapleiadene and 7-acetyl-9,11-di-tert-butyl-2,4,6-trimethyl-7H-12-oxa-3,7-diazapleiadene were determined by X-ray analysis. DI: /S Reactions of sterically hindered 1,2-benzoquinones with 2-methylquinoline and 2-methylbenzimidazole derivatives and 1,2,3-trimethylbenzimidazolium iodide lead to formation of unexpected products, such as 2-hetaryl-substituted 3-hydroxytropones [1, 2], polycyclic isoquinolines [3], and spirocyclic 1,3-benzodioxole derivatives [4]. For example, ring expansion in 1,2-benzoquinone gives rise to 3-hydroxytropones [5]. However, substituted 5-amino-2-methylquinolines Ia Ic reacted with 3,5-di-tert-butyl-1,2-benzoquinone (II) to give 7H-12-oxa-3,7-diazapleiadene derivatives IIIa IIIc in which 1,5-benzoxazepine fragment is peri-fused to quinoline ring [6], whereas no expected 3-hydroxytropones IV were formed (Scheme 1). Presumably, the formation of 7H-12-oxa-3,7-diazapleiadenes III is controlled by kinetic factor. There are no published data on the structure of peri-fused systems including a 1,4-oxazepine ring. With a view to study the structure of such compounds in more detail, we synthesized 7H-12-oxa-3,7-diazapleiadenes IIIa Scheme 1. R 1 R 2 H 2 Cl + t-bu t-bu H R 1 R 2 Ia Ic II IIIa IIIc H 2 Cl R 1 R 2 H IV R 1 = R 2 = H (a); R 1 =, R 2 = H (b); R 1 = H, R 2 = (c). 1329

2 1330 TKACHEV et al. IIIa IIIc Ac 2, Δ, 2 3 h Scheme 2. t-bu IIIc, and their subsequent treatment with acetic anhydride gave a series of 7-acetyl-12-oxa-3,7-diazapleiadene derivatives Va Vc (Scheme 2). The molecular and crystalline structures of 9,11-di-tert-butyl-2,4-dimethyl-7H-12-oxa-3,7-diazapleiadene (IIIa) and 7-acetyl-9,11-di-tert-butyl-2,4,6-trimethyl-7H-12-oxa- 3,7-diazapleiadene (Vb) were determined by X-ray analysis (Figs. 1, 2); the principal bond lengths and bond angles in molecules IIIa and Vb are collected in Tables 1 and 2. Molecule IIIa is folded along the 1 2 axis, so that the dihedral angle between the 1 2 C 10 C 15 and R 1 R 2 Va Vc R 1 = R 2 = H (a); R 1 =, R 2 = H (b); R 1 = H, R 2 = (c). Ac 1 2 C 3 C 4 C 5 planes is 38.5, and the 1 and 2 atoms deviate from the plane formed by the C 10 C 15, C 18, and C 19 atoms (mean-square deviation Å) by 0.17 and 0.15 Å, respectively, toward one side. The C 1 C 9, 1, C 16, and C 17 atoms lie in one plane within Å, while the 1 and 2 atoms deviate from that plane by 0.18 and 0.22 Å, respectively, toward opposite sides. Molecule Vb in which hydrogen atom on 2 is replaced by acetyl group is characterized by extended 2 C 5 and 2 C 15 bonds [1.436(3) and 1.436(3) Å against 1.396(4) and 1.392(3) Å in molecule IIIa, respectively], which may be due to redistribution of electron density as a result of amide conjugation between the C 19 = 2 double bond and lone electron pair on 2 [the C 19 = 2 bond length is 1.211(3) Å]. The 1 and 2 atoms lie in the plane formed by the C 10 C 15, C 21, and C 22 atoms (mean-square deviation Å) with an accuracy of and Å, and the dihedral angle between the 1 2 C 10 C 15 and 1 2 C 3 C 4 C 5 planes in Vb is increased to bviously, this is the result of introduction of a large (as compared to hydrogen atom) acetyl group and steric hindrances created thereby. The lower (Fig. 2) part of the molecule is also slightly strained: the C 1 C 9, 1, C 16, and C 17 atoms lie in one plane within Å, and the 1 and C 21 C 6 C 20 C 22 C 14 C 7 C 19 2 C 13 C 12 C 15 C 10 C 11 1 C 5 C 4 C3 C 8 C 9 1 C 18 C 2 C 1 C 23 C 24 C 15 C 20 C C 2 C 16 C 18 C 27 C 6 2 C 7 C 31 C 28 C 14 C 13 1 C 5 C 4 C3 C 8 C 26 C 32 C 33 C 9 12 C C C C 11 C 2 C 1 C 25 C 24 C 23 C 16 C 17 C 17 Fig. 1. Structure of the molecule of 9,11-di-tert-butyl-2,4- dimethyl-7h-quinolino[4,5-bc][1,5]benzoxazepine (IIIa) according to the X-ray diffraction data. Fig. 2. Structure of the molecule of 1-(9,11-di-tert-butyl- 2,4,6-trimethyl-7H-quinolino[4,5-bc][1,5]benzoxazepin-7- yl)ethan-1-one (Vb) according to the X-ray diffraction data.

3 SYTHESIS AD STRUCTURE F 7H-12-XA-3,7-DIAZAPLEIADEES 1331 Table 1. Selected bond lengths (d) and bond angles (ω) in the molecule of 9,11-di-tert-butyl-2,4-dimethyl-7H-quinolino- [4,5-bc][1,5]benzoxazepine (IIIa) Bond d, Å Bond d, Å Bond d, Å Bond d, Å 1 C (3) C 8 C (4) 1 C (3) C 10 C (4) 1 C (4) C 10 C (4) 1 C (3) C 11 C (4) 2 C (4) C 11 C (4) 2 C (3) C 12 C (4) C 1 C (4) C 13 C (4) C 1 C (4) C 13 C (4) C 2 C (4) C 14 C (4) C 3 C (4) C 18 C (5) C 4 C (3) C 18 C (5) C 4 C (3) C 18 C (4) C 5 C (4) C 19 C (6) C 6 C (4) C 19 C (6) C 7 C (4) C 19 C (5) C 8 C (4) Angle ω, deg Angle ω, deg Angle ω, deg Angle ω, deg C 3 1 C (2) 1 C 10 C (2) 2 C 1 C (2) C 12 C 11 C (3) C 1 2 C (2) C 12 C 11 C (2) C 2 C 1 C (3) C 10 C 11 C (2) 2 C 1 C (3) C 13 C 12 C (3) C 2 C (2) C 14 C 13 C (3) C 3 C 2 C (3) C 14 C 13 C (3) 1 C 3 C 124.2(2) C 12 C 13 C (3) C 2 C 3 C (2) C 13 C 14 C (3) C 5 C 4 C (2) C 10 C (2) C 5 C 4 C (2) C 10 C 15 C (2) C 6 C (2) 1 C 15 C (2) C 3 C 4 C (2) C 11 C 18 C (3) 1 C 5 C (2) C 11 C 18 C (3) C 6 C 5 C (2) C 25 C 18 C (3) C 8 C 7 C (3) C 11 C 18 C (3) C 5 C 6 C (2) C 25 C 18 C (3) C 7 C 8 C (3) C 24 C 18 C (3) C 7 C 8 C (2) C 20 C 19 C (4) 2 C 9 C (2) C 20 C 19 C (3) C 9 C 8 C (2) C 21 C 19 C (4) C 8 C 9 C (2) C 20 C 19 C (3) 2 C 9 C (2) C 21 C 19 C (3) C 15 C 10 C (2) C 22 C 19 C (3) C 15 C (2) C 15 1 C (2) 2 atoms deviate from that plane by and Å, respectively, toward opposite sides. The tertbutyl group on C 13 is disordered by two positions at a ratio of 0.85 : The dihedral angles between the 1 C 10 C 15 2 and 1 C 3 C 4 C 5 2 planes in molecules IIIa and Vb are and 124.9, respectively. Figure 3 illustrates variations in the structure of IIIa upon substitution of hydrogen on 2 by acetyl group; it shows molecules IIIa and Vb superimposed over each other at the plane passing through the 1, 2, C 12, and C 13 atoms. Carbon atoms in the tert-butyl groups of Vb in the less populated positions and hydrogen atoms (except for 2 H) are not shown. The distance between the 1 and 2 atoms in IIIa is Å, and the corresponding distance in molecule Vb is Å; the 2 atoms in both molecules deviate from the plane formed by the three neighboring atoms by and Å, and the sum of bond angles at the 2 atom is and 358.5, respectively. Molecules IIIa in crystal (Fig. 4) are linked to infinite chains along the c axis via intermolecular hydrogen bonds 2 H 1 (2.34 Å), whereas molecules of Vb in a unit cell are arranged in such a way that the minimal distance between the 2 atom of one molecule and hydrogen atom on C 2 in the neighboring molecule is Å. EXPERIMETAL The 1 H MR spectra were recorded on a Varian Unity-300 spectrometer; the chemical shifts were determined relative to tetramethylsilane as internal reference. The mass spectra were obtained on a Finnigan MAT ICS 50 mass spectrometer. The IR spectra were measured on a Varian 3100FT-IR Excalibur Series instrument with the use of an ATR accessory. The melting points were determined in glass capillaries on a PTP melting point apparatus and were not corrected.

4 1332 TKACHEV et al. C H C 7A C 6 C 7 C 20 C13 C 12 C 8A Fig. 3. Superposition of molecules IIIa and Vb at the plane passing through the 1, 2, C 12, and C 13 atoms. a C 8 b 0 1 C 4 C 2 C 9 1A Fig. 4. Chains formed by molecules IIIa in crystal via weak intermolecular hydrogen bonds. X-Ray analysis of compound IIIa. The unit cell parameters and reflection intensities (three-dimensional set) were determined on an Enraf onius CAD-4 diffractometer (λmok α irradiation, graphite monochromator) from a mm yellow transparent single crystal of IIIa. Monoclinic crystal system, C 25 H 30 2, M ; unit cell parameters: a = (5), b = (3), c = (5) Å; β = (3), V = (14) Å 3 ; Z = 4; d calc = g cm 3 ; μ(mok α ) = 0.66 mm 1 ; space group P2 1 /c. Intensities of 4130 reflections were measured in the range 2θ (ω/2θ-scanning). Averaging of equivalent reflection intensities gave 3956 independent reflections, 2219 of which were characterized by F 2 > 4σ(F 2 ). The structure was solved by the direct method using SHELXTL software package [7] and was refined by the full-matrix least-squares procedure with respect 1 c to F 2 in anisotropic approximation for non-hydrogen atoms (SHELXTL [7]). All hydrogen atoms in the crystalline structure of IIIa were localized by Fourier difference syntheses of electron density. The coordinates and thermal parameters of all hydrogen atoms (except for 1 H which was refined in isotropic approximation), were calculated by the least-squares procedure according to the riding model [7]. The absolute shifts of all 257 varied parameters of structure IIIa in the last cycle of full-matrix refinement were less than 0.001σ. The final divergence factors were R 1 = for reflections with I 2σ(I) and R 1 = 0.12 for all reflections; goodness of fit X-Ray analysis of compound Vb. The unit cell parameters and reflection intensities (three-dimensional set) were determined on a Kuma-Diffraction KM-4 diffractometer from a mm colorless transparent single crystal of Vb. Monoclinic crystal system, C 28 H , M ; unit cell parameters: a = (5), b = (3), c = (5) Å; β = (19) ; V = 5172(2) Å 3 ; Z = 8; d calc = g/cm 3 ; μ(mok α ) = 0.69 mm 1 ; space group I2/a. Intensities of 5390 reflections were measured in the range 2θ 52 by ω/2θ-scanning. After averaging of equivalent reflections, the array of measured F 2 hkl and σ(f 2 ) included 5085 independent reflections, 1966 of which were characterized by F 2 > 4σ(F 2 ). The structure was solved by the direct method and was refined with respect to F 2 by the full-matrix least-squares procedure in anisotropic approximation for non-hydrogen atoms using SHELXTL software package [7]. All hydrogen atoms in the crystalline structure of Vb were localized by Fourier difference syntheses of electron density. Their coordinates and isotropic thermal parameters were calculated by the least-squares procedure according to the riding model [7]. The absolute shifts of all 302 varied parameters of structure Vb in the last iteration were less than 0.001σ. The final divergence factors were R 1 = for reflections with I 2σ(I) and R 1 = 0.20 for all reflections; goodness of fit Compounds IIIa IIIc were synthesized according to the procedure described in [6]. 1-(9,11-Di-tert-butyl-2,4-dimethyl-7H-quinolino- [4,5-bc][1,5]benzoxazepin-7-yl)ethan-1-one (Va). A solution of 1.87 g (5 mmol) of 9,11-di-tert-butyl-2,4- dimethyl-7h-12-oxa-3,7-diazapleiadene (IIIa) in 15 ml of acetic anhydride was heated for 3 h under reflux. The mixture was cooled, diluted with water, and extracted with chloroform. The extract was evaporated, and the residue was recrystallized from propan-

5 SYTHESIS AD STRUCTURE F 7H-12-XA-3,7-DIAZAPLEIADEES 1333 Table 2. Selected bond lengths (d) and bond angles (ω) in the molecule of 1-(9,11-di-tert-butyl-2,4,6-trimethyl-7H-quinolino- [4,5-bc][1,5]benzoxazepin-7-yl)ethan-1-one (Vb) Bond d, Å Bond d, Å Bond d, Å Bond d, Å 1 C (3) C 10 C (3) 1 C (4) C 10 C (4) 2 C (3) C 11 C (4) 2 C (3) C 11 C (4) 1 C (4) C 12 C (4) 2 C (3) C 13 C (3) 2 C (3) C 13 C (4) C 1 C (5) C 14 C (3) C 1 C (5) C 19 C (4) C 3 C (4) C 21 C (6)0 C 2 C (4) C 21 C (5) C 4 C (4) C 21 C (5) C 4 C (4) C 21 C (2)0 C 6 C (4) C 21 C (6) C 5 C (4) C 21 C (3)0 C 7 C (5) C 22 C (5) C 6 C (4) C 22 C (5) C 8 C (4) C 22 C (5) C 8 C (5) 1 C (3) Angle ω, deg Angle ω, deg Angle ω, deg Angle ω, deg C 3 1 C (19) C 14 C 13 C (2) C 1 1 C (3) C 12 C 13 C (2) C 19 2 C (2) C 15 C 14 C (2) C 19 2 C (2) C 10 C 15 C (2) C 15 2 C (19) C 10 C (2) 1 C 1 C (3) C 14 C (2) 1 C 1 C (3) 2 C (3) C 2 C 1 C (4) 2 C 19 C (3) C 3 C 2 C (3) 2 C 19 C (2) C 2 C (3) C 33 C 21 C (2).0 C 2 C 3 C (3) C 33 C 21 C 26 56(3). 1 C 3 C (2) C 27 C 21 C (4) C 5 C 4 C (3) C 33 C 21 C (2) C 5 C 4 C (2) C 27 C 21 C (3) C 9 C 4 C (3) C 26 C 21 C (3) C 6 C 5 C (2) C 33 C 21 C (3).0 C 6 C (2) C 27 C 21 C (12) C 4 C (2) C 26 C 21 C (10) C 5 C 6 C (3) C 13 C 21 C (10) C 5 C 6 C (3) C 33 C 21 C (2).0 C 7 C 6 C (3) C 27 C 21 C (5) C 8 C 7 C (3) C 26 C 21 C (4) C 7 C 8 C (3) C 13 C 21 C (3) C 7 C 8 C (4) C 32 C 21 C (12) C 9 C 8 C (4) C 33 C 21 C (3).0 1 C 9 C (3) C 27 C 21 C (12) 1 C 9 C (3) C 26 C 21 C (12) C 4 C 9 C (3) C 13 C 21 C (11) C 15 C (2) C 32 C 21 C (17) C 15 C 10 C (2) C 28 C 21 C (11) 1 C 10 C (2) C 23 C 22 C (3) C 12 C 11 C (2) C 23 C 22 C (3),0 C 12 C 11 C (3) C 25 C 22 C (3) C 10 C 11 C (3) C 23 C 22 C (3),0 C 13 C 12 C (2) C 25 C 22 C (3) C 14 C 13 C (2) C 11 C 22 C (3) 0 2-ol. Yield 1.5 g (72%), light yellow crystals, mp C (from propan-2-ol). IR spectrum, ν, cm 1 : 1678, 1604, 1504, 1473, 1444, 1425, 1385, 1369, 1344, 1318, 1260, 1232, 1206, 1162, 1138, 1057, 1019, H MR spectrum (CDCl 3 ), δ, ppm: 1.31 s (9H, 9-t-Bu), 1.49 s (9H, 11-t-Bu), 2.00 s (3H, CH 3 C), 2.73 s (6H, 2-CH 3, 4-CH 3,), m (5H, H arom ). Mass spectrum, m/z (I rel, %): 416 (10) [M] +, 374 (35), 359 (4), 343 (2), 329 (2), 315 (3), 301 (5), 287 (4), 273 (5), 259 (5), 245 (3), 233 (4), 115 (3), 91 (2), 77 (3), 57 (15), 43 (70). Found, %: C 77.72; H 7.58; C 27 H Calculated, %: C 77.85; H 7.74; Compounds Vb and Vc were synthesized in a similar way. 1-(9,11-Di-tert-butyl-2,4,6-trimethyl-7H-quinolino[4,5-bc][1,5]benzoxazepin-7-yl)ethan-1-one (Vb) was synthesized from 1.94 g of compound IIIb. Yield 1.25 g (58%), light yellow crystals, mp C. IR spectrum, ν, cm 1 : 1678, 1606, 1567, 1475, 1423, 1392, 1365, 1339, 1325, 1307, 1256, 1241, 1225, 1208, 1176, 1155, 1057, 1033, 1003, H MR spectrum (CDCl 3 ), δ, ppm: 1.31 s (9H, 9-t-Bu), 1.47 s (9H, 11-t-Bu), 2.00 s (3H, CH 3 C), 2.48 s (3H, 4-CH 3 ), 2.69 s (3H, 6-CH 3 ), 2.73 s (3H, 2-CH 3 ), 7.12

6 1334 TKACHEV et al m (4H, H arom ). Mass spectrum, m/z (I rel, %): 430 (4) [M] +, 388 (7), 371 (2), 357 (2), 315 (2), 299 (2), 287 (3), 273 (3), 257 (2), 247 (3), 231 (2), 115 (3), 91 (2), 77 (3), 57 (7), 43 (50). Found, %: C 77.94; H 7.82; C 28 H Calculated, %: C 78.10; H 7.96; (9,11-Di-tert-butyl-2,4,5-trimethyl-7H-quinolino[4,5-bc][1,5]benzoxazepin-7-yl)ethan-1-one (Vc) was synthesized from 1.94 g of compound IIIc. Yield 1.1 g (51%), light yellow crystals, mp C. IR spectrum, ν, cm 1 : 1683, 1608, 1556, 1510, 1471, 1442, 1424, 1376, 1365, 1332, 1318, 1298, 1227, 1211, 1178, 1159, 1129, 1100, 1051, 1031, 1009, H MR spectrum (CDCl 3 ), δ, ppm: 1.31 s (9H, 9-t-Bu), 1.48 s (9H, 11-t-Bu), 2.00 s (3H, CH 3 C), 2.49 s (3H, 5-CH 3 ), 2.67 s (3H, 4-CH 3 ), 2.70 s (3H, 2-CH 3 ), m (4H, H arom ). Mass spectrum, m/z (I rel, %): 430 (5) [M] +, 388 (10), 373 (2), 357 (3), 315 (2), 301 (3), 287 (2), 273 (3), 259 (2), 247 (2), 232 (2), 115 (3), 91 (3), 77 (2), 57 (5), 43 (60). Found, %: C 77.98; H 7.80; C 28 H Calculated, %: C 78.10; H 7.96; This study was performed under financial support by the Presidium of the Russian Academy of Sciences (program no. 7, Development of thods for Preparation of Chemical Substances and Design of ew Materials, subprogram Development of thodology of rganic Synthesis and Design of Compounds with Important Practical Properties, program for support of young scientists, and program for support of leading scientific schools, project no. Sh ). REFERECES 1. Sayapin, Yu.A., Komissarov, V.., Minkin, V.I., Tkachev, V.V., Aldoshin, S.M., and Shilov, G.V., Russ. J. rg. Chem., 2005, vol. 41, p Sayapin, Yu.A., Komissarov, V.., Duong ghia Bang, Dorogan, I.V., Minkin, V.I., Tkachev, V.V., Shilov, G.V., Aldoshin, S.M., and Charushin, V.., ndeleev Commun., 2008, vol. 18, p Minkin, V.I., Komissarov, V.., and Sayapin, Yu.A., Arkivoc, 2006, part (vii), p Komissarov, V.., Sayapin, Yu.A., Minkin, V.I., Tkachev, V.V., Aldoshin, S.M., and Shilov, G.V., Russ. J. rg. Chem., 2007, vol. 43, p Minkin, V.I., Aldoshin, S.M., Komissarov, V.., Dorogan, I.V., Sayapin, Yu.A., Tkachev, V.V., and Starikov, A.G., Izv. Ross. Akad. auk, Ser. Khim., 2006, p Duong ghia Bang, Komissarov, V.., Sayapin, Yu.A., Tkachev, V.V., Shilov, G.V., Aldoshin, S.M., and Minkin, V.I., Russ. J. rg. Chem., 2009, vol. 45, p Sheldrick, G.M., SHELXTL v. 6.14, Structure Determination Software Suite, Madison, Wisconsin, USA: Bruker AXS, 2000.