{2,7-Dieth­oxy-8-[(naphthalen-2-yl)carbon­yl]naphthalen-1-yl}(naphthalen-2-yl)methanone

Takehiro Tsumuki; Akiko Okamoto; Hideaki Oike; Noriyuki Yonezawa

doi:10.1107/S1600536813003577

. 2013 Feb 9;69(Pt 3):o369. doi: 10.1107/S1600536813003577

{2,7-Diethoxy-8-[(naphthalen-2-yl)carbonyl]naphthalen-1-yl}(naphthalen-2-yl)methanone

Takehiro Tsumuki ^a, Akiko Okamoto ^a,^*, Hideaki Oike ^a, Noriyuki Yonezawa ^a

PMCID: PMC3588451 PMID: 23476558

Abstract

In the title compound, C₃₆H₂₈O₄, the two 2-naphthoyl groups at the 1- and 8-positions of the central 2,7-diethoxynaphthalene ring system are aligned almost antiparallel and make a dihedral angle of 48.35 (5)°. The dihedral angles between the central 2,7-diethoxynaphthalene ring system and the terminal naphthalene ring systems are 77.64 (4) and 73.73 (4)°. In the crystal, molecules are linked into chains along the a-axis direction by dual C—H⋯O interactions between naphthoyl groups.

Related literature

For electrophilic aroylation of naphthalene derivatives, see: Okamoto & Yonezawa (2009 ▶); Okamoto et al. (2011 ▶). For the structures of closely related compounds, see: Nakaema et al. (2008 ▶); Tsumuki et al. (2011 ▶); Sasagawa et al. (2012 ▶); Isogai et al. (2013 ▶); Yoshiwaka et al. (2013 ▶). graphic file with name e-69-0o369-scheme1.jpg

Experimental

Crystal data

C₃₆H₂₈O₄
M _r = 524.58
Monoclinic,
a = 7.86946 (14) Å
b = 27.1458 (5) Å
c = 12.8490 (2) Å
β = 102.267 (1)°
V = 2682.16 (8) Å³
Z = 4
Cu Kα radiation
μ = 0.67 mm⁻¹
T = 193 K
0.50 × 0.25 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.732, T _max = 0.878
41696 measured reflections
4914 independent reflections
3996 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.097
S = 1.09
4914 reflections
364 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku, 2010 ▶); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Click here for additional data file.^{(26.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813003577/rz5043sup1.cif

e-69-0o369-sup1.cif^{(26.7KB, cif)}

Click here for additional data file.^{(235.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813003577/rz5043Isup2.hkl

e-69-0o369-Isup2.hkl^{(235.8KB, hkl)}

Click here for additional data file.^{(10.2KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813003577/rz5043Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C21—H21⋯O3ⁱ	0.95	2.45	3.3958 (18)	173
C25—H25⋯O4ⁱⁱ	0.95	2.45	3.3996 (18)	176

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors express their gratitude to Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture & Technology, for technical advice. This work was partially supported by an Iron and Steel Institute of Japan (ISIJ) Research Promotion Grant.

supplementary crystallographic information

Comment

In the course of our study on selective electrophilic aromatic aroylation of the naphthalene ring core, 1,8-diaroylnaphthalene compounds have proved to be formed regioselectively by the aid of a suitable acidic mediator (Okamoto & Yonezawa, 2009, Okamoto et al., 2011). Recently, we have reported the crystal structures of several 1,8-diaroylated naphthalene analogues exemplified by 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008), [2,7-dimethoxy-8-(2-naphthoyl)naphthalen-1-yl](naphthalen-2-yl)methanone (Tsumuki et al., 2011), {2,7-dimethoxy-8-[4-(2-methylpropyl)benzoyl]naphthalen-1-yl}[4-(2-methylpropyl) phenyl]methanone (Sasagawa et al., 2012), (8-benzoyl-2,7-diethoxynaphthalen-1-yl)(phenyl)methanone (Isogai et al., 2013), and [8-(4-phenoxybenzoyl)-2,7-bis(propan-2-yloxy)naphthalen-1-yl](4-phenoxyphenyl) methanone (Yoshiwaka et al., 2013). The most simple analogues in these compounds, 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008) and [2,7-dimethoxy-8-(2-naphthoyl)naphthalen-1-yl](naphthalen-2-yl)methanone (Tsumuki et al., 2011), lie across a crystallographic 2-fold axis and the molecular packing are stabilized by C—H···O interactions and π···π interactions between the aroyl groups. As a part of our ongoing studies on the molecular structures of these kinds of homologous molecules, the X-ray crystal structure of the title compound is reported on herein.

The molecular structure of the title molecule is illustrated in Fig. 1. The two terminal naphthoyl groups are situated in an opposite direction and twisted away from the central 2,7-diethoxynaphthalene unit. The dihedral angles between the two naphthalene rings of the terminal naphthoyl groups (C13—C22 and C23—C32) is 48.35 (5)°. The dihedral angles between the terminal napthalene rings and the central naphthalene ring (C1—C10) are 77.64 (4) and 73.73 (4)°. The torsion angles between the carbonyl moieties and the central naphthalene ring are -52.63 (18)° [C9—C1—C11—O3] and -58.16 (17)° [C9—C8—C12—O4]. On the other hand, the carbonyl groups are slightly twisted away from the attached terminal naphthalene rings [torsion angles O3—C11—C13—C14 = -21.17 (19)° and O4—C12—C23—C32 = -14.10 (19)°]. In the crystal, the molecular packing of the title compound is mainly stabilized by two C—H···O interactions between the naphthoyl moieties leading to the formation of chains along the a axis (Table 1 and Fig. 2).

Experimental

To a solution of 2-naphthoyl chloride (14.3 g, 75.0 mmol) and TiCl₄ (42.7 g, 225 mmol) in CH₂Cl₂ (62.5 ml), 2,7-diethoxynaphthalene (5.4 g, 25.3 mmol) was added. The reaction mixture was stirred at r. t. for 24 h, then poured into ice-cold water (200 ml). The aqueous layer was extracted with CHCl₃ (60 ml × 3). The combined organic extracts were washed with 2M aqueous NaOH (80 ml × 3) followed by washing with brine (80 ml × 3). The organic layer was dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give a cake (yield 97%). The crude product was purified by recrystallization from chloroform/methanol (1:2 v/v) solution (isolated yield 70%). Furthermore, the isolated product was crystallized from chloroform to give single crystals suitable for X-ray analysis.

¹H NMR δ (500 MHz, CDCl₃): 0.86 (6H, t, J = 6.9 Hz), 3.96 (4H, q, J = 6.9), 7.21 (2H, d, J = 9.0 Hz), 7.39 (2H, t, J = 7.5 Hz), 7.47 (2H, t, J = 7.5 Hz), 7.69–7.93 (8H, m), 7.98 (2H, d, J = 9.0 Hz), 8.15 (2H, s) p.p.m.; ¹³C NMR δ (125 MHz, CDCl₃): 14.36, 64.93, 112.35, 122.03, 124.89, 125.56, 125.89, 127.47, 127.54, 127.70, 129.59, 130.44, 130.74, 132.08, 132.41, 135.43, 136.47, 155.97, 197.17 p.p.m.; IR (KBr): 1658, 1623, 1608, 1510, 1470, 1275 cm^-1; HRMS (m/z): [M+H]+ calcd. for C₃₆H₂₉O₄, 525.2066; found, 525.2031.