organic compounds
Isopropyl 3,4-dihydroxybenzoate
aCollege of Life Sciences, Northwest University, Xi'an 710069, People's Republic of China, bCollege of Chemistry & Chemical Engineering, Xian Shiyou University, Xi'an 710065, People's Republic of China, and cCollege of Life Sciences and Key Laboratory of Resource Biology and Biotechnology in Western China, Ministry of Education, Northwest University, Xi'an 710069, People's Republic of China
*Correspondence e-mail: zhengxh@nwu.edu.cn
In the 10H12O4, O—H⋯O hydrogen bonds incorporating R22(10) and R22(14) motifs link molecules into chains along [10]. An intramolecular O—H⋯O hydrogen bond is also observed.
of the title compound, CRelated literature
The title compound is a derivative of protocatechuic acid (3,4-dihydroxybenzoic acid). For the properties of et al. (2004); Yun-Choi et al. (1996); Robert et al. (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995).
of protocatechuic acid, see: ShizukaExperimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536811044965/lh5339sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811044965/lh5339Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536811044965/lh5339Isup3.cml
To a solution of 0.1M protocatechuic acid in 500 ml of 2-propanol at room temperature, 0.01M TsOH in 2-propanol was added. After the solution had been allowed to stir and reflux for 16 h, the solvent was removed under reduced pressure. The residue was extracted with ethyl acetate three times and filtered. The filtrate was washed successively with dilute saturated aqueous NaHCO3 solution, saturated aqueous NaCl, dried over MgSO4, and evaporated. The crude product was purified by χm-1): 3458, 3314, 2985, 2957, 1677, 1609, 1531, 1445, 1378, 1347, 1299, 1238, 1165, 1101; 1H NMR (DMSO, δ, p.p.m.): 9.539 (s, 1 H), 9.536 (s, 1 H), 7.363—7.366(d, 1 H), 7.299—7.316 (dd, 1 H), 6.804—7.818 (d, 1 H), 5.037—5.079(m, 1 H), 1.285 (s, 3 H), 1.275 (s, 3 H).
(SiO2; elution with petroleum ether-acetoacetate, 6:1 v/v). Yield 30%. X-ray quality crystals were grown from a solution of the title compound in acetone and toluene at room temperature. Spectroscopic analysis: IR(KBr,All H atoms were visible in difference maps but were included in calculated positions with C—H = 0.93 - 0.98Å, O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C) or 1.2Ueq(Cmethyl,O).
Esters of protocatechuic acid has been shown to have, a DPPH radical scavenging ability, anti-thrombotic activity, and can act as inhibitors of the sn-glycerol-3-phosphate oxidase of Trypanosoma brucei brucei (Shizuka et al., 2004; Yun-Choi et al., 1996; Robert et al., 1986).
The molecular structure of the title compound (I) is shown in Fig. 1. Intramolecular O—H···O hydrogen bonds form R22(10) and R22(14) motifs (Bernstein et al., 1995). In the crystal, intermolecular O—H···O hydrogen bonds link molecules into chains propagating along [110] (see Fig. 2).
The title compound is a derivative of protocatechuic acid (3,4-dihydroxybenzoic acid). For the properties of
of protocatechuic acid, see: Shizuka et al. (2004); Yun-Choi et al. (1996); Robert et al. (1986). For hydrogen-bond motifs, see: Bernstein et al. (1995).Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 30% probability level. | |
Fig. 2. Part of the crystal structure of (I) with Hydrogen bonds shown as dashed lines. |
C10H12O4 | Z = 2 |
Mr = 196.20 | F(000) = 208 |
Triclinic, P1 | Dx = 1.306 Mg m−3 |
Hall symbol: -P 1 | Melting point: 407(1) K |
a = 5.8485 (12) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.1844 (17) Å | Cell parameters from 666 reflections |
c = 9.9834 (19) Å | θ = 2.4–24.2° |
α = 72.629 (3)° | µ = 0.10 mm−1 |
β = 80.547 (3)° | T = 296 K |
γ = 78.980 (3)° | Needle, colorless |
V = 499.06 (17) Å3 | 0.37 × 0.25 × 0.15 mm |
Bruker APEXII CCD diffractometer | 1289 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.012 |
Graphite monochromator | θmax = 25.1°, θmin = 2.2° |
φ and ω scans | h = −6→6 |
2520 measured reflections | k = −10→10 |
1745 independent reflections | l = −9→11 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0685P)2 + 0.037P] where P = (Fo2 + 2Fc2)/3 |
1745 reflections | (Δ/σ)max < 0.001 |
131 parameters | Δρmax = 0.13 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C10H12O4 | γ = 78.980 (3)° |
Mr = 196.20 | V = 499.06 (17) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.8485 (12) Å | Mo Kα radiation |
b = 9.1844 (17) Å | µ = 0.10 mm−1 |
c = 9.9834 (19) Å | T = 296 K |
α = 72.629 (3)° | 0.37 × 0.25 × 0.15 mm |
β = 80.547 (3)° |
Bruker APEXII CCD diffractometer | 1289 reflections with I > 2σ(I) |
2520 measured reflections | Rint = 0.012 |
1745 independent reflections |
R[F2 > 2σ(F2)] = 0.048 | 0 restraints |
wR(F2) = 0.133 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.13 e Å−3 |
1745 reflections | Δρmin = −0.23 e Å−3 |
131 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.2571 (2) | 0.15042 (14) | 0.29888 (13) | 0.0554 (4) | |
O2 | −0.0069 (2) | 0.13603 (15) | 0.16625 (15) | 0.0666 (5) | |
O3 | 0.7691 (2) | −0.42927 (15) | 0.09653 (16) | 0.0672 (5) | |
H3 | 0.7088 | −0.4623 | 0.0452 | 0.101* | |
O4 | 0.3545 (3) | −0.32701 (15) | −0.01531 (15) | 0.0667 (5) | |
H4 | 0.2461 | −0.2741 | −0.0586 | 0.100* | |
C1 | −0.0633 (5) | 0.2409 (3) | 0.4524 (3) | 0.0925 (9) | |
H1A | −0.1650 | 0.1839 | 0.4288 | 0.139* | |
H1B | −0.1541 | 0.3308 | 0.4754 | 0.139* | |
H1C | 0.0143 | 0.1771 | 0.5321 | 0.139* | |
C2 | 0.2856 (5) | 0.3780 (3) | 0.3562 (3) | 0.0811 (7) | |
H2A | 0.3599 | 0.3182 | 0.4385 | 0.122* | |
H2B | 0.2030 | 0.4736 | 0.3715 | 0.122* | |
H2C | 0.4024 | 0.3988 | 0.2762 | 0.122* | |
C3 | 0.1158 (4) | 0.2893 (2) | 0.3288 (2) | 0.0605 (6) | |
H3A | 0.0369 | 0.3511 | 0.2462 | 0.073* | |
C4 | 0.1778 (3) | 0.0861 (2) | 0.21617 (18) | 0.0471 (5) | |
C5 | 0.3358 (3) | −0.05140 (19) | 0.19011 (18) | 0.0436 (4) | |
C6 | 0.2685 (3) | −0.12546 (19) | 0.10392 (18) | 0.0463 (5) | |
H6 | 0.1255 | −0.0895 | 0.0673 | 0.056* | |
C7 | 0.4099 (3) | −0.25143 (19) | 0.07177 (18) | 0.0469 (5) | |
C8 | 0.6225 (3) | −0.3068 (2) | 0.12786 (19) | 0.0485 (5) | |
C9 | 0.6887 (3) | −0.2345 (2) | 0.2151 (2) | 0.0553 (5) | |
H9 | 0.8301 | −0.2720 | 0.2534 | 0.066* | |
C10 | 0.5479 (3) | −0.1072 (2) | 0.2463 (2) | 0.0521 (5) | |
H10 | 0.5949 | −0.0590 | 0.3047 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0583 (9) | 0.0500 (8) | 0.0628 (8) | 0.0063 (6) | −0.0190 (7) | −0.0256 (6) |
O2 | 0.0620 (9) | 0.0635 (9) | 0.0807 (10) | 0.0197 (7) | −0.0336 (8) | −0.0342 (8) |
O3 | 0.0612 (9) | 0.0555 (8) | 0.0889 (11) | 0.0185 (7) | −0.0253 (8) | −0.0338 (7) |
O4 | 0.0740 (11) | 0.0547 (8) | 0.0803 (10) | 0.0211 (7) | −0.0381 (8) | −0.0354 (8) |
C1 | 0.0704 (16) | 0.107 (2) | 0.116 (2) | −0.0091 (14) | 0.0063 (15) | −0.0656 (18) |
C2 | 0.0992 (19) | 0.0651 (14) | 0.0901 (17) | −0.0163 (13) | −0.0072 (14) | −0.0374 (13) |
C3 | 0.0705 (14) | 0.0491 (11) | 0.0651 (13) | 0.0111 (10) | −0.0207 (11) | −0.0265 (10) |
C4 | 0.0507 (11) | 0.0447 (10) | 0.0442 (10) | −0.0008 (8) | −0.0102 (8) | −0.0110 (8) |
C5 | 0.0439 (10) | 0.0397 (9) | 0.0434 (10) | −0.0011 (8) | −0.0072 (8) | −0.0077 (8) |
C6 | 0.0433 (10) | 0.0438 (10) | 0.0492 (10) | 0.0045 (8) | −0.0136 (8) | −0.0115 (8) |
C7 | 0.0518 (11) | 0.0398 (10) | 0.0491 (10) | 0.0002 (8) | −0.0119 (8) | −0.0133 (8) |
C8 | 0.0461 (11) | 0.0407 (10) | 0.0540 (11) | 0.0027 (8) | −0.0091 (8) | −0.0101 (8) |
C9 | 0.0452 (11) | 0.0516 (11) | 0.0684 (13) | 0.0057 (9) | −0.0203 (9) | −0.0166 (9) |
C10 | 0.0521 (11) | 0.0488 (11) | 0.0580 (11) | −0.0020 (9) | −0.0159 (9) | −0.0172 (9) |
O1—C4 | 1.330 (2) | C2—H2B | 0.9600 |
O1—C3 | 1.464 (2) | C2—H2C | 0.9600 |
O2—C4 | 1.215 (2) | C3—H3A | 0.9800 |
O3—C8 | 1.361 (2) | C4—C5 | 1.479 (2) |
O3—H3 | 0.8200 | C5—C6 | 1.386 (2) |
O4—C7 | 1.372 (2) | C5—C10 | 1.389 (3) |
O4—H4 | 0.8200 | C6—C7 | 1.377 (2) |
C1—C3 | 1.497 (3) | C6—H6 | 0.9300 |
C1—H1A | 0.9600 | C7—C8 | 1.391 (3) |
C1—H1B | 0.9600 | C8—C9 | 1.380 (3) |
C1—H1C | 0.9600 | C9—C10 | 1.381 (3) |
C2—C3 | 1.502 (3) | C9—H9 | 0.9300 |
C2—H2A | 0.9600 | C10—H10 | 0.9300 |
C4—O1—C3 | 118.03 (14) | O2—C4—O1 | 123.08 (16) |
C8—O3—H3 | 109.5 | O2—C4—C5 | 123.18 (17) |
C7—O4—H4 | 109.5 | O1—C4—C5 | 113.73 (15) |
C3—C1—H1A | 109.5 | C6—C5—C10 | 119.21 (16) |
C3—C1—H1B | 109.5 | C6—C5—C4 | 117.83 (16) |
H1A—C1—H1B | 109.5 | C10—C5—C4 | 122.95 (17) |
C3—C1—H1C | 109.5 | C7—C6—C5 | 121.01 (16) |
H1A—C1—H1C | 109.5 | C7—C6—H6 | 119.5 |
H1B—C1—H1C | 109.5 | C5—C6—H6 | 119.5 |
C3—C2—H2A | 109.5 | O4—C7—C6 | 123.48 (16) |
C3—C2—H2B | 109.5 | O4—C7—C8 | 116.86 (15) |
H2A—C2—H2B | 109.5 | C6—C7—C8 | 119.66 (16) |
C3—C2—H2C | 109.5 | O3—C8—C9 | 119.09 (16) |
H2A—C2—H2C | 109.5 | O3—C8—C7 | 121.41 (16) |
H2B—C2—H2C | 109.5 | C9—C8—C7 | 119.49 (16) |
O1—C3—C1 | 108.46 (17) | C8—C9—C10 | 120.90 (17) |
O1—C3—C2 | 105.88 (17) | C8—C9—H9 | 119.6 |
C1—C3—C2 | 113.43 (18) | C10—C9—H9 | 119.6 |
O1—C3—H3A | 109.7 | C9—C10—C5 | 119.73 (18) |
C1—C3—H3A | 109.7 | C9—C10—H10 | 120.1 |
C2—C3—H3A | 109.7 | C5—C10—H10 | 120.1 |
C4—O1—C3—C1 | 85.7 (2) | C5—C6—C7—C8 | 0.8 (3) |
C4—O1—C3—C2 | −152.21 (17) | O4—C7—C8—O3 | 0.6 (3) |
C3—O1—C4—O2 | −0.9 (3) | C6—C7—C8—O3 | −178.80 (16) |
C3—O1—C4—C5 | 178.76 (15) | O4—C7—C8—C9 | 179.39 (17) |
O2—C4—C5—C6 | 0.3 (3) | C6—C7—C8—C9 | 0.0 (3) |
O1—C4—C5—C6 | −179.44 (15) | O3—C8—C9—C10 | 178.19 (17) |
O2—C4—C5—C10 | 179.34 (18) | C7—C8—C9—C10 | −0.6 (3) |
O1—C4—C5—C10 | −0.4 (3) | C8—C9—C10—C5 | 0.5 (3) |
C10—C5—C6—C7 | −1.0 (3) | C6—C5—C10—C9 | 0.3 (3) |
C4—C5—C6—C7 | 178.12 (15) | C4—C5—C10—C9 | −178.72 (17) |
C5—C6—C7—O4 | −178.53 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4i | 0.82 | 2.15 | 2.844 (2) | 142 |
O3—H3···O4 | 0.82 | 2.28 | 2.720 (2) | 115 |
O4—H4···O2ii | 0.82 | 1.93 | 2.747 (2) | 175 |
Symmetry codes: (i) −x+1, −y−1, −z; (ii) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C10H12O4 |
Mr | 196.20 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 5.8485 (12), 9.1844 (17), 9.9834 (19) |
α, β, γ (°) | 72.629 (3), 80.547 (3), 78.980 (3) |
V (Å3) | 499.06 (17) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.37 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2520, 1745, 1289 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.133, 1.04 |
No. of reflections | 1745 |
No. of parameters | 131 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.13, −0.23 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O4i | 0.820 | 2.150 | 2.844 (2) | 142.27 |
O3—H3···O4 | 0.820 | 2.276 | 2.720 (2) | 114.47 |
O4—H4···O2ii | 0.820 | 1.929 | 2.747 (2) | 175.23 |
Symmetry codes: (i) −x+1, −y−1, −z; (ii) −x, −y, −z. |
Acknowledgements
The authors are grateful for financial support from the National Natural Sciences Foundation of China (grant No. 20875074), the Higher Specialized Research Fund for the Doctoral Program (grant Nos. 20106101110001 and 20106101120024), the Important Science & Technology Specific Projects of the Innovative Program of Shannxi Province (grant No. 2010ZDKG-46) and the Scientific Research Foundation for PhDs of Xi'an Shiyou University (grant No. 2011BS004).
References
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Esters of protocatechuic acid has been shown to have, a DPPH radical scavenging ability, anti-thrombotic activity, and can act as inhibitors of the sn-glycerol-3-phosphate oxidase of Trypanosoma brucei brucei (Shizuka et al., 2004; Yun-Choi et al., 1996; Robert et al., 1986).
The molecular structure of the title compound (I) is shown in Fig. 1. Intramolecular O—H···O hydrogen bonds form R22(10) and R22(14) motifs (Bernstein et al., 1995). In the crystal, intermolecular O—H···O hydrogen bonds link molecules into chains propagating along [110] (see Fig. 2).