[8-(4-But­oxy­benzo­yl)-2,7-dimeth­oxy­naphthalen-1-yl](4-but­oxy­phen­yl)methanone

Kosuke Sasagawa; Toyokazu Muto; Akiko Okamoto; Hideaki Oike; Noriyuki Yonezawa

doi:10.1107/S1600536811048550

. 2011 Nov 19;67(Pt 12):o3354. doi: 10.1107/S1600536811048550

[8-(4-Butoxybenzoyl)-2,7-dimethoxynaphthalen-1-yl](4-butoxyphenyl)methanone

Kosuke Sasagawa ^a, Toyokazu Muto ^a, Akiko Okamoto ^a,^*, Hideaki Oike ^a, Noriyuki Yonezawa ^a

PMCID: PMC3238999 PMID: 22199848

Abstract

The molecule of the title compound, C₃₄H₃₆O₆, is located on a twofold rotation axis. The two 4-butoxybenzoyl groups at the 1- and 8-positions of the naphthalene ring system are aligned almost antiparallel. The dihedral angles between the benzene rings and the naphthalene ring system are 71.70 (4)°. In the crystal, the molecules are connected via C—H⋯π interactions into a layer parallel to (010).

Related literature

For electrophilic aromatic aroylation of the naphthalene core, see: Okamoto & Yonezawa (2009 ▶); Okamoto et al. (2011 ▶). For the structures of closely related compounds, see: Hijikata et al. (2010 ▶); Muto et al. (2010 ▶); Nakaema et al. (2008 ▶); Watanabe et al. (2010 ▶); Sasagawa et al. (2011 ▶).

Experimental

Crystal data

C₃₄H₃₆O₆
M _r = 540.63
Orthorhombic,
a = 11.0930 (2) Å
b = 20.0537 (3) Å
c = 13.1409 (2) Å
V = 2923.26 (8) Å³
Z = 4
Cu Kα radiation
μ = 0.67 mm⁻¹
T = 193 K
0.60 × 0.40 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.689, T _max = 0.878
50625 measured reflections
2679 independent reflections
2542 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.105
S = 1.04
2679 reflections
185 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.16 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

Crystal structure: contains datablock(s) 1_8-obu-shelxl, global, I. DOI: 10.1107/S1600536811048550/gk2430sup1.cif

e-67-o3354-sup1.cif^{(19.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811048550/gk2430Isup2.hkl

e-67-o3354-Isup2.hkl^{(129KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811048550/gk2430Isup3.cml

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

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

Cg is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯Cgⁱ	0.98	2.68	3.5056 (14)	142

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors express their gratitude to Master Daichi Hijikata, Department of Organic and Polymer Materials Chemistry, Graduate School, Tokyo University of Agriculture & Technology, and Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture and Technology, for their technical advice.

supplementary crystallographic information

Comment

In the course of our study on electrophilic aromatic aroylation of the naphthalene 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 X-ray crystal structures of 1,8-diaroylated 2,7-dimethoxynaphthalene derivatives such as 1,8-dibenzoyl-2,7-dimethoxynaphthalene (Nakaema et al., 2008), (2,7-dimethoxynaphthalene-1,8-diyl)bis(4-fluorophenyl)dimethanone [1,8-bis(4-fluorobenzoyl)-2,7-dimethoxynaphthalene] (Watanabe, Nagasawa et al., 2010), 1,8-bis(4-methylbenzoyl)-2,7-dimethoxynaphthalene (Muto et al., 2010), and {8-[4-(bromomethyl)benzoyl]-2,7-dimethoxynaphthalen-1-yl}[4-(bromomethyl)phenyl]methanone [1,8-bis(4-bromomethylbenzoyl)-2,7-dimethoxynaphthalene] (Sasagawa et al., 2011). The aroyl groups in these compounds are perpendicularly attached to the naphthalene rings and oriented in opposite directions. On the other hand, X-ray structure of 2,7-dimethoxy-1,8-bis(4-phenoxybenzoyl)naphthalene (Hijikata et al., 2010) having the aroyl groups oriented in the same directions has been also revealed. As a part of our ongoing studies on the molecular structures of this kind of homologous molecules, the X-ray crystal structure of title compound, 1,8-diaroylnaphthalene bearing butoxy groups, is discussed in this article.

The molecular structure of the title compound is displayed in Fig 1. The molecule of (I) lies on a crystallographic 2-fold axis so that the asymmetric unit contains one-half of the molecule. Thus, two 4-butoxybenzoyl groups are situated in anti orientation and are twisted away from the attached naphthalene ring. The dihedral angle between the best planes of the 4-butoxyphenyl groups and the naphthalene ring system is 71.70 (4)°.

The dihedral between the naphthalene ring system and the bridging carbonyl C—C(═O)—C plane is 77.60 (5)° [C5—C6—C8—O2 torsion angle = -77.75 (12)°], far larger than that [8.64 (5)°; C12—C10—C8—O2 torsion angle = 8.33 (14)°] between the phenyl group and the bridging carbonyl group.

In the crystal, molecules are arranged into (0 1 0) layers via C-H···π interactions (Fig. 2).

Experimental

The title compound was prepared by S_N2 reaction of 1,8-bis(4-hydroxybenzoyl)-2,7-dimethoxynaphthalene (1.0 mmol, 428.5 mg), which was obtained via S_NAr reaction of 1,8-bis(4-fluorobenzoyl)-2,7-dimethoxynaphthalene with sodium hydroxide, with bromobutane (3.0 mmol, 411 mg) and potassium carbonate (2.8 mmol, 387 mg) in N,N-dimethylformamide (DMF; 2.5 ml). After the reaction mixture was stirred at 333 K for 6 h, it was poured into water (30 ml) and the mixture was extracted with CHCl₃ (15 ml × 3). The combined extracts were washed with brine. The organic layers thus obtained were dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give cake (96% yield). The crude product was purified by recrystallization from methanol (isolated yield 65%). Furthermore, the isolated product was crystallized from methanol to give single crystal. Spectroscopic data:¹H NMR δ(300 MHz, CDCl₃); 0.98(6H, t, J = 7.2), 1.49(4H, m, J = 7.5 Hz), 1.77(4H, q, J = 8.1 Hz), 3.70(6H, s), 3.98(4H, m), 6.80(4H, broad), 7.20(2H, d, J = 9.0 Hz), 7.65(4H, broad), 7.92(2H, d, J = 9.3 Hz) p.p.m.. ¹³C NMR δ(100 MHz, CDCl₃); 13.8, 19.2, 31.2, 56.5, 67.7, 111.3, 113.4, 122.0, 125.6, 129.6, 131.4, 131.6, 131.8, 155.9, 162.7, 194.9 p.p.m.. IR (KBr); 2956, 2936, 1665, 1600, 1509, 1267, 1250 cm^-1. (m/z): [M + H]⁺ Calcd for C₃₄H₃₇O₆, 541.2590; found, 541.2559. m.p. = 392–399.9 K