2-(2-Methyl­naphtho[2,1-b]furan-1-yl)acetic acid

Martyn Jevric; Dennis K Taylor; Edward R T Tiekink

doi:10.1107/S1600536808015572

. 2008 May 30;64(Pt 6):o1167. doi: 10.1107/S1600536808015572

2-(2-Methylnaphtho[2,1-b]furan-1-yl)acetic acid

Martyn Jevric ^a, Dennis K Taylor ^b,^‡, Edward R T Tiekink ^c,^*

PMCID: PMC2961634 PMID: 21202674

Abstract

In the title molecule, C₁₅H₁₂O₃, the two six-membered and one five-membered fused-ring system is almost planar and the CH₂C(=O)OH residue is essentially orthogonal to it. In the crystal structure, centrosymmetric dimers are formed via the carboxylic acid {⋯O=C—O—H}₂ synthon.

Related literature

For related literature, see: Haselgrove et al. (1999 ▶); Jevric et al. (2001 ▶).

Experimental

Crystal data

C₁₅H₁₂O₃
M _r = 240.25
Monoclinic,
a = 31.380 (3) Å
b = 4.8370 (4) Å
c = 15.7885 (13) Å
β = 98.087 (2)°
V = 2372.6 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 223 (2) K
0.49 × 0.36 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
9334 measured reflections
3445 independent reflections
2790 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.138
S = 1.04
3445 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT and SHELXTL (Sheldrick, 2008 ▶); program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808015572/lh2631sup1.cif

e-64-o1167-sup1.cif^{(15.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808015572/lh2631Isup2.hkl

e-64-o1167-Isup2.hkl^{(169.1KB, hkl)}

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
O12—H12⋯O11ⁱ	0.83	1.83	2.6553 (14)	170
C21—H21B⋯O12ⁱⁱ	0.97	2.52	3.2663 (19)	134

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

Acknowledgments

We are grateful to the Australian Research Council for financial support.

supplementary crystallographic information

Comment

The effective dehydrogenation of diastereomeric mixture of 1, Fig. 3, to form the aromatized tricyclic 2 could be effected with the use of DDQ in THF under reflux conditions (Haselgrove et al., 1999). Crystals of the title acid derivative (I) were obtained by base hydrolysis of 2 in methanol solution (Jevric et al., 2001).

The tricyclic system in (I), Fig. 1, comprises six- (A), six- (B), and five-membered rings (C) with the sequence of dihedral angles between their respective least-squares planes being 1.48 (6), 2.34 (6), 0.91 (6) ° for A/B, A/C, and B/C, respectively. The CH₂C(=O)OH residue is essentially orthogonal to this aromatic system as seen in the C1/C11/C12/O11 torsion angle of -165.68 (9)°. Centrosymmetrically related molecules associate into dimers via the familiar eight-membered carboxylic acid {···O=C—O—H}₂ synthon, Table 1. Each dimer thus formed is associated to two other molecules, each related by 2-fold symmetry, via C—H···O contacts. These consolidate molecules into a 2-D array in the bc-plane as shown in Fig. 2.

Experimental

To a stirring solution of 1 (Fig. 3, 1.91 g, 7.46 mmol) in anhydrous THF (50 ml) was added DDQ (1.81 g, 7.97 mmol) and the reaction brought to reflux for 24 h under a nitrogen atmosphere. The solution was allowed to cool to room temperature, diluted with water and extracted twice with dichloromethane. The organic phase was dried (MgSO₄), filtered and volatiles removed in vacuo. The crude residue was purified by column chromatography (10% acetone in hexane) to give pure methyl 2-(2-methylnaphtho[2,1-b]furan-1-yl)acetate, 2, as a yellow solid, m.p: 349 - 351 K. R_f 0.41 (10% acetone in hexane). IR (CH₂Cl₂, cm^-1) 1738, 1620, 1581, 1525, 804. ¹H NMR (CDCl₃, 300 MHz) δ 2.25 (s, 3H), 3.70 (s, 3H), 3.98 (s, 2H), 7.45–7.48 (m, 1H), 7.56–7.60 (m, 2H), 7.65–7.68 (m, 1H), 7.92–7.94 (m, 1H), 8.23–8.26 (m, 1H) p.p.m.. ¹³C NMR (CDCl₃, 50 MHz) δ 12.0, 31.5, 52.2, 109.5, 112.1, 122.2, 122.8, 124.0, 124.6, 126.1, 128.0, 129.0, 130.8, 151.5, 152.2, 171.6 p.p.m.. MS m/z (%): 254 (M+, 76), 95 (100), 181 (31), 165 (27), 152 (22). HRMS, C₁₆H₁₄O₃: calcd, 254.0943. Found 254.0942.

Compound (I) was obtained by the base hydrolysis of 2 in methanol solution. The colourless solid was recrystallized from ethanol solution in 75% yield; m.p.: 451 - 455 K (decomposes, sealed tube). IR (nujol, cm^-1) 1699, 1622, 1579, 1525. ¹H NMR (CDCl₃, 300 MHz) δ 2.51 (s, 3H), 4.00 (s, 2H), 7.44–7.69 (m, 4H), 7.91–7.94 (m, 1H), 8.21–8.23 (m, 1H) p.p.m.. ¹³C NMR (CDCl₃, 50 MHz) δ 11.9, 31.1, 108.8, 112.1, 122.0, 122.7, 124.0, 126.2, 127.9, 129.1, 130.8, 151.6, 152.4, 175.5 (1 masked carbon) p.p.m.. MS m/z (%): 240 (M+, 39), 195 (100), 165 (13), 152 (13), 69 (37). Elemental analysis found: C, 74.92; H, 4.98%. C₁₅H₁₂O₃ requires C, 74.99; H, 5.03%.