(2,7-Dimeth­oxy­naphthalen-1-yl)(4-fluoro­phen­yl)methanone

Shoji Watanabe; Toyokazu Muto; Atsushi Nagasawa; Akiko Okamoto; Noriyuki Yonezawa

doi:10.1107/S1600536811018332

. 2011 May 20;67(Pt 6):o1466. doi: 10.1107/S1600536811018332

(2,7-Dimethoxynaphthalen-1-yl)(4-fluorophenyl)methanone

Shoji Watanabe ^a, Toyokazu Muto ^a, Atsushi Nagasawa ^a, Akiko Okamoto ^a,^*, Noriyuki Yonezawa ^a

PMCID: PMC3120321 PMID: 21754837

Abstract

In the title compound, C₁₉H₁₅FO₃, the dihedral angle between the naphthalene ring system and the benzene ring is 80.46 (4)°. In the crystal, molecules are linked by intermolecular C—H⋯O hydrogen bonds into chains parallel to the b axis.

Related literature

For the formation reaction of aroylated naphthalene compounds via electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene, see: Okamoto & Yonezawa (2009 ▶). For related structures reported by our group, see: Kato et al. (2010 ▶); Muto et al. (2010 ▶); Watanabe, Nagasawa et al. (2010 ▶); Watanabe, Nakaema, Muto et al. (2010 ▶); Watanabe, Nakaema, Nishijima et al. (2010 ▶).

Experimental

Crystal data

C₁₉H₁₅FO₃
M _r = 310.31
Monoclinic,
a = 10.9714 (2) Å
b = 7.51791 (14) Å
c = 18.7832 (3) Å
β = 99.917 (1)°
V = 1526.13 (5) Å³
Z = 4
Cu Kα radiation
μ = 0.82 mm⁻¹
T = 193 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T _min = 0.735, T _max = 0.853
26625 measured reflections
2789 independent reflections
2566 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.109
S = 1.01
2789 reflections
211 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP (Burnett & Johnson, 1996 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018332/rz2596sup1.cif

e-67-o1466-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018332/rz2596Isup2.hkl

e-67-o1466-Isup2.hkl^{(134.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811018332/rz2596Isup3.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
C14—H14⋯O1ⁱ	0.95	2.35	3.2139 (15)	151

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors would express their gratitude to Professor Keiichi Noguchi, Instrumentation Analysis Center, Tokyo University of Agriculture & Technology, for his technical advice. This work was partially supported by the Mukai Science and Technology Foundation, Tokyo, Japan.

supplementary crystallographic information

Comment

In the course of our study on electrophilic aromatic aroylation of 2,7-dimethoxynaphthalene, peri-aroylnaphthalene compounds have proven to be formed regioselectively with the aid of suitable acidic mediators (Okamoto & Yonezawa, 2009). The aroyl groups at the 1,8-positions of the naphthalene rings in these compounds are twisted almost perpendicularly but the benzene ring moieties of the aroyl groups tilt slightly toward the exo sides of the naphthalene rings. Recently, we reported the structures of 1,8-diaroyl-2,7-dimethoxynaphthalenes, i. e., (2,7-dimethoxynaphthalene-1,8-diyl)bis(4-fluorophenyl)dimethanone (Watanabe, Nagasawa et al., 2010), bis(4-bromophenyl)(2,7-dimethoxynaphthalene-1,8-diyl)dimethanone (Watanabe, Nakaema, Muto et al., 2010), and [2,7-dimethoxy-8-(4-methylbenzoyl)-1-naphthyl](4-methylphenyl)methanone (Muto et al., 2010). Furthermore, the crystal structures of 1-aroyl-2,7-dimethoxynaphthalenes, i. e., 2,7-dimethoxy-1-(4-nitrobenzoyl)naphthalene (Watanabe, Nakaema, Nishijima et al., 2010) and (2,7-dimethoxynaphthalen-1-yl)(phenyl)methanone (Kato et al., 2010), also exhibit essentially the same non-coplanar structure as the 1,8-diaroylated naphthalenes. As a part of our ongoing studies on the formation and the structure of the aroylated naphthalene derivatives, the synthesis and crystal structure of (I), a 1-monoaroylnaphthalene bearing fluoro group, is discussed in this report. (I) was prepared by electrophilic aromatic aroylation reaction of 2,7-dimethoxynaphthalene with 4-fluorobenzoyl chloride.

The molecular structure of (I) is displayed in Fig. 1. The interplanar angle between the benzene ring (C12—C17) and the naphthalene ring (C1—C10) is 80.46 (4)°. The torsion angle between the carbonyl group and the naphthalene ring [C10–C1–C11–O1 = -77.77 (13)°] is larger than that between the carbonyl group and fluorophenyl ring [O1–C11–C12–C17 = 4.20 (15)°].

In the crystal packing, the molecules are aligned consecutively in stacks along the b axis (Fig. 2). This stack of naphthalene rings occludes the adjacent counter part and vice versa. The crystal packing is stabilized by weak intermolecular C—H···O hydrogen bond between the hydrogen atom of the 4-fluorophenyl group and the carbonyl oxygen atom (Table 1; Fig. 3).

Experimental

The title compound was prepared by treatment of a mixture of 2,7-dimethoxynaphthalene (75.29 mg, 0.4 mmol), 4-fluorobenzoyl chloride (69.77 mg, 0.44 mmol), CH₂Cl₂ (1 ml) with AlCl₃ (0.48 mmol, 64.00 mg). After the reaction mixture was stirred at 273 K for 3 h, the mixture was poured into ice-cooled water and extracted with CHCl₃ (10 ml × 3). The combined extracts were washed with 2 M aqueous NaOH followed by washing with brine. The organic layer thus obtained was dried over anhydrous MgSO₄. The solvent was removed under reduced pressure to give cake. The crude product was purified by recrystallization from ethanol (isolated yield 76%). Colourless platelet single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution (m.p. 381 K). Anal. Calcd for C₁₉H₁₅O₃F: C, 73.54; H, 4.87. Found: C, 73.45; H, 4.83. Spectroscopic data:

¹H NMR (300 MHz, CDCl₃. p.p.m.) 3.67 (3H, s), 3.75 (3H, s), 6.79 (1H, d, J = 2.4 Hz), 6.70 (1H, dd, J = 9.0, 2.4 Hz), 7.07 (2H, dd, J = 9.0, 9.0 Hz), 7.12 (1H, d, J = 9.0 Hz), 7.69 (1H, d, J = 9.0 Hz), 7.83 (1H, d, J = 9.0 Hz), 7.87 (2H, dd, J = 5.7, 8.7 Hz);

¹³C NMR (75.0 MHz, CDCl₃, p.p.m.); 55.2945, 56.4131, 102.1511, 110.2777, 115.7894 (J_C–F = 22.39 Hz), 117.2283, 121.4923, 124.5039, 129.8388, 131.2824, 132.3007 (J_C–F = 9.39 Hz), 133.0798, 134.6669 (J_C–F = 2.88 Hz), 155.0597, 159.0656, 166.0784 (J_C–F = 255.03 Hz), 196.5529;

IR (KBr, cm^-1): 1662, 1627, 1597, 1513, 1279, 1242;