3-[(R)-1-Hy­droxy­butan-2-yl]-1,2,3-benzo­triazin-4(3H)-one

Fernando Rocha-Alonzo; David Morales-Morales; Simón Hernández-Ortega; Reyna Reyes-Martínez; Miguel Parra-Hake

doi:10.1107/S1600536812043802

. 2012 Oct 31;68(Pt 11):o3240–o3241. doi: 10.1107/S1600536812043802

3-[(R)-1-Hydroxybutan-2-yl]-1,2,3-benzotriazin-4(3H)-one

Fernando Rocha-Alonzo ^a,^*, David Morales-Morales ^b, Simón Hernández-Ortega ^b, Reyna Reyes-Martínez ^b, Miguel Parra-Hake ^c,^*

PMCID: PMC3515319 PMID: 23284539

Abstract

The crystal structure of the title compound, C₁₁H₁₃N₃O₂, is stabilized by O—H⋯O hydrogen bonds, which link the molecules into chains along [100].

Related literature

For biological and synthetic applications of benzo-1,2,3-triazinones, see: Caliendo et al. (1999 ▶); Zheng et al. (2005 ▶); Vaisburg et al. (2004 ▶); Chollet et al. (2002 ▶); Le Diguarher et al. (2003 ▶); Clark et al. (1995 ▶); Carpino et al. (2004 ▶); Janout et al. (2003 ▶); Gierasch et al. (2000 ▶). For structures of benzo-1,2,3-triazinones, see: Hjortås et al. (1973 ▶); Hunt et al. (1983 ▶); Reingruber et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the synthesis, see: Gómez et al. (2005 ▶).

Experimental

Crystal data

C₁₁H₁₃N₃O₂
M _r = 219.24
Orthorhombic,
a = 8.9668 (13) Å
b = 10.1506 (15) Å
c = 12.0238 (17) Å
V = 1094.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.32 × 0.10 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
9057 measured reflections
2000 independent reflections
1700 reflections with I > 2σ(I)
R _int = 0.044

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.076
S = 0.93
2000 reflections
149 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(15.4KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812043802/zj2097sup1.cif

e-68-o3240-sup1.cif^{(15.4KB, cif)}

Click here for additional data file.^{(98.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043802/zj2097Isup2.hkl

e-68-o3240-Isup2.hkl^{(98.4KB, hkl)}

Click here for additional data file.^{(4.6KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812043802/zj2097Isup3.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
O2—H2⋯O1ⁱ	0.85 (1)	2.03 (1)	2.8712 (19)	171 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge support for this project by the Consejo Nacional de Ciencia y Tecnología (CONACyT grant 36435-E) and Consejo del Sistema Nacional de Educación Tecnológica (COSNET) grant 486–02-P. The authors are indebted to Adrián Ochoa Terán and Ignacio Rivero Espejel for their analytical support of this work.

supplementary crystallographic information

Comment

Benzo-1,2,3-triazinones are compounds widely investigated for their potential biological and chemical properties. These heterocyclic compounds have been studied as anesthetic (Caliendo et al., 1999), anti-inflammatory (Zheng et al., 2005), anticancer (Vaisburg et al.., 2004; Chollet et al., 2002), and antitumoural (Le Diguarher et al., 2003; Clark et al., 1995) agents. In organic synthesis, 1,2,3-triazinones are used as an activating moiety in coupling agents for the preparation of peptides and amino acids (Carpino et al., 2004; Janout et al., 2003; Gierasch et al., 2000). As result of its biological and synthetic importance, we have developed an alternative method for obtaining compounds with 1,2,3-triazinone moiety and in this paper we are describing the crystal structure of the title compound (I, Figure 1).

In the molecular structure of I, the N1=N2 bond [1.2636 (17) Å] is longer than the typical values for N=N double bonds (1.236 Å), whereas the N2–N3 bond [1.3735 (18) Å] is shorter than typical values for a N–N single bonds (1.404 Å) (Allen et al.., 1987). The structure of I shows co-planarity between two rings (1.30°). These measurements are in agreement with other benzo-1,2,3-triazinone crystal structure reports (Hjortås et al., 1973; Hunt et al., 1983; Reingruber et al., 2009). Of interest to pharmaceutical applications, it has been suggested that co-planar structure in benzo-1,2,3-triazinones could give DNA-intercalating abilities such as those displayed by some anticancer agents (Reingruber et al., 2009).

In the crystal structure, adjacent units are arranged into one-dimensional chain along [100] direction via O–H···O intermolecular hydrogen bonds (Figure 2 and Table 1).

Experimental

The synthesis of the tittle compound included reagents and solvents of reagent grade, which were used without further purification. To a solution of 2-[(4R)-4-ethyl-4,5-dihydro-1,3-oxazol-2-yl]aniline (Gómez et al., 2005) (0.89 g, 4.7 mmol, dissolved in 85 ml of methanol) was slowly added isoamyl nitrite (4.40 g, 37.6 mmol, 8 equiv) and the reaction mixture was stirred at room temperature until the disappearance of the aniline (followed by TLC, hexane/ethyl acetate, 3:1). The solvent was evaporated under reduced pressure to give a crude product that was purified by washing with petroleum ether and recrystallization from hexane/ethyl acetate. Crystalline colorless prisms of I were grown by slow diffusion of hexane over saturated ethyl acetate solutions of I. Yield > 99%, based on 2-[(4R)-4-Ethyl-4,5-dihydro-1,3-oxazol-2-yl]aniline; m.p., 89–90 °C. = -5.45° (c 0.22, MeOH). FTIR (KBr pellet, cm^-1): 3439, 1686, 1663, 1296. ¹H NMR [(CD₃)₂CO, 200 MHz] d 8.29 (ddd, J = 0.6, 1.5, 7.9 Hz, 2H), 8.16 (ddd, J = 0.6, 1.5, 8.1 Hz, 2H), 8.07 (ddd, J = 1.5, 7.0, 8.2 Hz, 2H), 7.91 (ddd,, J = 1.5, 7.0, 7.9 Hz, 2H), 5.22 (ddd, J = 5.1, 7.6, 15.5 Hz, 2H), 4.10 (dd, J = 8.4, 11.3 Hz, 2H), 3.96 (dd, J = 5.1, 11.3 Hz, 2H), 1.99 (dd, J = 7.5, 15.0 Hz, 4H), 0.90 (t, J = 7.4 Hz, 6H). ¹³C NMR [(CD₃)₂CO, 50 MHz] d 156.6, 144.5, 135.8, 133.2, 128.8, 125.7, 120.3, 64.2, 62.3, 24.2, 10.8. ESI-HRMS:220.1091 (100), calculated for [M+H]⁺, C₁₁H₁₄N₃O₂⁺, 220.1081; 192.1025 (8), calculated for [M+H—N₂]⁺, C₁₁H₁₄NO₂⁺, 192.1019. Anal for C₁₁H₁₃N₃O₂ (% Calcd./found) C, 60.26/60.73; H, 5.98/6.45; N, 19.17/19.47.