3-Anilinomethyl-5-chloro-1,3-­benzoxazol-2(3H)-one

Abdullah Aydın; Zeynep Soyer; Mehmet Akkurt; Orhan Büyükgüngör

doi:10.1107/S1600536812017709

. 2012 Apr 28;68(Pt 5):o1544–o1545. doi: 10.1107/S1600536812017709

3-Anilinomethyl-5-chloro-1,3-benzoxazol-2(3H)-one

Abdullah Aydın ^a,^*, Zeynep Soyer ^b, Mehmet Akkurt ^c, Orhan Büyükgüngör ^d

PMCID: PMC3344645 PMID: 22590407

Abstract

In the title compound, C₁₄H₁₁ClN₂O₂, the 2,3-dihydro-1,3-benzoxazole ring system is essentially planar [maximum deviation = 0.009 (2) Å] and makes a dihedral angle of 79.15 (7)° with the phenyl ring. Intermolecular N—H⋯O and weak C—H⋯Cl hydrogen bonds occur in the crystal structure.

Related literature

For the synthesis and biological activity of compounds with a benzoxazolone nucleus, see; Varma & Nobles (1968 ▶); Courtois et al. (2004 ▶); Deng et al. (2006 ▶); Ivanova et al. (2007 ▶); Koksal et al. (2002 ▶, 2005 ▶); Onkol et al. (2001 ▶); Soyer et al. (2005 ▶); Ucar et al. (1998 ▶); Unlu et al. (2003 ▶). For bond-length data, see: Allen et al. (1987 ▶). For a related structure, see: Aydın et al. (2004 ▶).

Experimental

Crystal data

C₁₄H₁₁ClN₂O₂
M _r = 274.70
Monoclinic,
a = 9.7379 (5) Å
b = 12.4797 (7) Å
c = 10.2392 (7) Å
β = 93.129 (5)°
V = 1242.48 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.80 × 0.48 × 0.26 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.837, T _max = 0.924
20574 measured reflections
3051 independent reflections
2544 reflections with I > 2σ(I)
R _int = 0.046

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.106
S = 1.07
3051 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017709/xu5511sup1.cif

e-68-o1544-sup1.cif^{(21.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017709/xu5511Isup2.hkl

e-68-o1544-Isup2.hkl^{(149.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812017709/xu5511Isup3.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
N2—H2A⋯O2ⁱ	0.86	2.30	3.1296 (17)	162
C11—H11⋯Cl1ⁱⁱ	0.93	2.70	3.5295 (17)	150

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

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

supplementary crystallographic information

Comment

The benzoxazolone nucleus represents an important pharmacophore present in pharmaceutical products. The compounds possessing this structure have a broad spectrum of biological activities, such as anti-HIV (Deng et al., 2006), anticancer (Ivanova et al., 2007), analgesic (Unlu et al., 2003), anti-inflammatory (Koksal et al., 2005), antinociceptive (Onkol et al., 2001), antimicrobial (Koksal et al., 2002), anticonvulsant (Ucar et al., 1998), antimalarial (Courtois et al., 2004), human leukocyte MPO clorinating inhibitor activity (Soyer et al., 2005).

In addition to, this compound was synthesized before by (Varma & Nobles, 1968) and they reported that most benzoxazolinone compounds have shown significant antibacterial activity.

In the title compound (I), (Fig. 1), the mean planes of the 2,3-dihydro-1,3-benzoxazole and phenyl rings make a dihedral angle of 79.15 (7)° with each other. The N1—C8—N2—C9 torsion angle is -72.99 (18)°. The bond lengths in (I) are normal and correspond to those observed in the related compound (Allen et al., 1987).

The Cl1—C3 and N1—C1 bond lengths are 1.7315 (16) Å, and 1.3914 (18) Å, respectively. The Cl1—C3—C4 and O2—C7—N1 bond angles are 118.73 (13) ° and 129.27 (15) °, respectively. The bond lengths and the bond angles of (I) are comparable to those observed in related structure (Aydın et al., 2004).

The crystal structure is stabilized by intermolecular N—H···O and C—H···Cl interactions (Table 1 and Fig. 2), connecting the molecules along the [001] direction.

Experimental

4-Chloro-2-aminophenol (10 mmol), urea (50 mmol) and 37% HCl (2.5 ml) were irradiated (300 W, 413 K) for 15 min in a microwave oven. After completion of reaction (by monitoring with TLC), water (10 ml) was added to the reaction mixture and stirred at room temperature for 1 h. The resulting precipitate was filtered and washed with water. The crude product crystallized from ethanol-water (1:1) to yield 5-chloro-2(3H)-benzoxazolone. This compound (2 mmol) was dissolved in methanol (5 ml). Aniline (2 mmol) and 37% formalin (2.5 mmol) were added to this solution. The mixture was stirred vigorously for 3 h. The resulting precipitate was filtered and washed with cold methanol. The crude product was crystallized from methanol.

M.p.: 463 K. Yield 84%; IR v_max (FTIR/ATR): 3398, 3066, 1750, 1604 cm^-1; ¹H-NMR (DMSO-d₆): δ 5.23 (2H, d, J=7.0 Hz, CH₂), 6.61(1H, t, J=7.4 Hz, H-Aniline), 6.73-6.75 (2H, m, H-Aniline), 6.96 (1H, t, J=7.3 Hz, NH), 7.09 (2H, t, J=7.4 Hz, H-Aniline) 7.14 (1H, dd, J=2.3; 8.6 Hz, H-Benzoxazolone), 7.31 (1H, d, J=8.6 Hz, H-Benzoxazolone), 7.70 (1H, d, J=2.3 Hz, H-Benzoxazolone) p.p.m.; MS (ESI) m/z (%): 275 (M+H, 11), 277 (M+H+2, 4).