organic compounds
1-(4-Benzyloxy-2-hydroxyphenyl)ethanone
aCollege of Life Sciences, Northwest A&F University, Yangling Shaanxi 712100, People's Republic of China, and bCollege of Science, Northwest A&F University, Yangling Shaanxi 712100, People's Republic of China
*Correspondence e-mail: mnathantuan@yahoo.com
The title compound, C15H14O3, has been obtained from the reaction of 2,4-dihydroxyacetophenone, potassium carbonate and benzyl bromide. The remaining hydroxy group is involved in an intramolecular O—H⋯O hydrogen bond. In the crystal, intermolecular C—H⋯O contacts occur.
Related literature
For background to the Williamson reaction in organic synthesis, see: Dermer (1934). For synthetic procedures for related compounds, see: Mendelson et al. (1996). For a related structure, see: Ma et al. (2010).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Siemens, 1996); cell SAINT (Siemens, 1996); 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); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S160053681104637X/im2328sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681104637X/im2328Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S160053681104637X/im2328Isup3.cml
2, 4-Dihydroxy-acetonephenone (4 mmol), potassium carbonate (8 mmol), benzyl bromide (4 mmol), and 40 ml acetone were mixed in a 100 ml flask. After 3 h stirring at 331 K, the crude product was obtained (yield: 78%). Single crystals were obtained by recrystallization from methanol.
The positions of all H atoms were fixed geometrically and refined using a riding model with C—H = 0.93–0.97 Å ,O—H= 0.82 Å, and Uiso(H) = 1.2–1.5 Ueq(C, O).
The Williamson reaction is a very useful transformation in organic synthesis since the products are of value in both industrial and academic applications. It usually involves the employment of an alkali-metal salt of the hydroxy compound and an alkyl halide (Dermer, 1934). Synthetic procedures to
derived from 2,4-dihydroxy-acetophenone as well as the structural characterisation of a related molecule have been described before (Mendelson et al., 1996; Ma et al., 2010).In this paper, we present the title compound, (I), which was synthesized by the reaction of 2, 4-dihydroxy-acetonephenone, potassium carbonate and benzyl bromide. In (I) (Fig. 1), the dihedral angle between the aromatic rings is 53.48 (4)°. The crystal packing exhibits no significantly short intermolecular contacts.
For background to the Williamson reaction in organic synthesis, see: Dermer (1934). For synthetic procedures for related compounds, see: Mendelson et al. (1996). For a related structure, see: Ma et al. (2010).
Data collection: SMART (Siemens, 1996); cell
SAINT (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level. | |
Fig. 2. Crystal packing of (I) viewed along the b axis, with hydrogen bonds shown as dashed lines. |
C15H14O3 | Z = 2 |
Mr = 242.26 | F(000) = 256 |
Triclinic, P1 | Dx = 1.301 Mg m−3 |
Hall symbol: -P 1 | Melting point = 378–379 K |
a = 5.8433 (7) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.0096 (8) Å | Cell parameters from 945 reflections |
c = 13.8089 (13) Å | θ = 2.7–25.4° |
α = 74.061 (1)° | µ = 0.09 mm−1 |
β = 84.589 (1)° | T = 298 K |
γ = 87.372 (2)° | Triclinic, colourless |
V = 618.54 (11) Å3 | 0.23 × 0.20 × 0.15 mm |
Siemens SMART CCD area-detector diffractometer | 2167 independent reflections |
Radiation source: fine-focus sealed tube | 1291 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
phi and ω scans | θmax = 25.0°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −6→6 |
Tmin = 0.980, Tmax = 0.987 | k = −9→9 |
3169 measured reflections | l = −16→15 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0468P)2] where P = (Fo2 + 2Fc2)/3 |
2167 reflections | (Δ/σ)max < 0.001 |
165 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.14 e Å−3 |
C15H14O3 | γ = 87.372 (2)° |
Mr = 242.26 | V = 618.54 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 5.8433 (7) Å | Mo Kα radiation |
b = 8.0096 (8) Å | µ = 0.09 mm−1 |
c = 13.8089 (13) Å | T = 298 K |
α = 74.061 (1)° | 0.23 × 0.20 × 0.15 mm |
β = 84.589 (1)° |
Siemens SMART CCD area-detector diffractometer | 2167 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1291 reflections with I > 2σ(I) |
Tmin = 0.980, Tmax = 0.987 | Rint = 0.026 |
3169 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.114 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.15 e Å−3 |
2167 reflections | Δρmin = −0.14 e Å−3 |
165 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 | 0.6013 (3) | 0.8182 (2) | −0.02477 (10) | 0.0812 (5) | |
O2 | 0.8544 (3) | 0.91909 (18) | 0.08846 (10) | 0.0723 (5) | |
H2 | 0.8070 | 0.9162 | 0.0349 | 0.108* | |
O3 | 0.6839 (2) | 0.71044 (16) | 0.44284 (9) | 0.0584 (4) | |
C1 | 0.2766 (4) | 0.6428 (3) | 0.03392 (16) | 0.0804 (7) | |
H1A | 0.2655 | 0.6613 | −0.0372 | 0.121* | |
H1B | 0.1382 | 0.6848 | 0.0635 | 0.121* | |
H1C | 0.2971 | 0.5210 | 0.0653 | 0.121* | |
C2 | 0.4770 (4) | 0.7384 (3) | 0.04958 (16) | 0.0627 (6) | |
C3 | 0.5296 (3) | 0.7344 (2) | 0.15150 (13) | 0.0499 (5) | |
C4 | 0.7175 (3) | 0.8243 (2) | 0.16617 (13) | 0.0529 (5) | |
C5 | 0.7750 (3) | 0.8181 (2) | 0.26222 (13) | 0.0520 (5) | |
H5 | 0.9021 | 0.8771 | 0.2705 | 0.062* | |
C6 | 0.6417 (3) | 0.7236 (2) | 0.34562 (13) | 0.0479 (5) | |
C7 | 0.4525 (3) | 0.6338 (2) | 0.33393 (14) | 0.0544 (5) | |
H7 | 0.3636 | 0.5700 | 0.3902 | 0.065* | |
C8 | 0.3993 (3) | 0.6409 (2) | 0.23848 (14) | 0.0566 (5) | |
H8 | 0.2719 | 0.5815 | 0.2310 | 0.068* | |
C9 | 0.8747 (3) | 0.8038 (3) | 0.45748 (14) | 0.0605 (6) | |
H9A | 0.8578 | 0.9257 | 0.4220 | 0.073* | |
H9B | 1.0162 | 0.7594 | 0.4301 | 0.073* | |
C10 | 0.8863 (3) | 0.7845 (2) | 0.56755 (14) | 0.0501 (5) | |
C11 | 0.7172 (3) | 0.8552 (3) | 0.62181 (15) | 0.0618 (6) | |
H11 | 0.5887 | 0.9088 | 0.5905 | 0.074* | |
C12 | 0.7353 (4) | 0.8478 (3) | 0.72185 (15) | 0.0655 (6) | |
H12 | 0.6197 | 0.8961 | 0.7574 | 0.079* | |
C13 | 0.9239 (4) | 0.7690 (3) | 0.76880 (16) | 0.0654 (6) | |
H13 | 0.9373 | 0.7646 | 0.8360 | 0.078* | |
C14 | 1.0919 (4) | 0.6970 (3) | 0.71643 (17) | 0.0688 (6) | |
H14 | 1.2196 | 0.6430 | 0.7482 | 0.083* | |
C15 | 1.0730 (4) | 0.7039 (3) | 0.61631 (15) | 0.0606 (6) | |
H15 | 1.1878 | 0.6535 | 0.5815 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.1067 (13) | 0.0896 (12) | 0.0446 (9) | 0.0045 (10) | −0.0021 (9) | −0.0160 (8) |
O2 | 0.0836 (10) | 0.0796 (11) | 0.0449 (8) | −0.0142 (8) | 0.0097 (7) | −0.0051 (7) |
O3 | 0.0708 (9) | 0.0625 (9) | 0.0418 (8) | −0.0226 (7) | −0.0022 (6) | −0.0115 (6) |
C1 | 0.0932 (18) | 0.0912 (18) | 0.0669 (15) | 0.0076 (15) | −0.0257 (13) | −0.0336 (13) |
C2 | 0.0768 (16) | 0.0593 (14) | 0.0544 (14) | 0.0154 (12) | −0.0087 (12) | −0.0211 (11) |
C3 | 0.0601 (13) | 0.0478 (12) | 0.0422 (12) | 0.0036 (10) | −0.0029 (9) | −0.0139 (9) |
C4 | 0.0627 (14) | 0.0488 (12) | 0.0410 (12) | 0.0001 (10) | 0.0065 (10) | −0.0057 (9) |
C5 | 0.0569 (13) | 0.0515 (12) | 0.0464 (12) | −0.0099 (10) | −0.0014 (10) | −0.0106 (9) |
C6 | 0.0593 (12) | 0.0441 (11) | 0.0385 (11) | −0.0048 (10) | 0.0007 (9) | −0.0096 (9) |
C7 | 0.0612 (13) | 0.0548 (13) | 0.0461 (12) | −0.0141 (10) | 0.0056 (10) | −0.0134 (9) |
C8 | 0.0581 (13) | 0.0589 (13) | 0.0558 (13) | −0.0075 (10) | −0.0035 (10) | −0.0202 (10) |
C9 | 0.0640 (14) | 0.0650 (14) | 0.0533 (13) | −0.0178 (11) | −0.0017 (10) | −0.0158 (10) |
C10 | 0.0537 (12) | 0.0511 (12) | 0.0466 (12) | −0.0088 (10) | −0.0041 (10) | −0.0137 (9) |
C11 | 0.0546 (13) | 0.0719 (15) | 0.0578 (14) | 0.0027 (11) | −0.0098 (10) | −0.0147 (11) |
C12 | 0.0641 (14) | 0.0770 (16) | 0.0577 (14) | −0.0032 (12) | 0.0022 (11) | −0.0245 (11) |
C13 | 0.0768 (16) | 0.0720 (16) | 0.0485 (13) | −0.0132 (13) | −0.0077 (12) | −0.0158 (11) |
C14 | 0.0660 (15) | 0.0761 (16) | 0.0606 (15) | 0.0005 (12) | −0.0168 (12) | −0.0088 (12) |
C15 | 0.0606 (14) | 0.0612 (14) | 0.0595 (14) | 0.0012 (11) | 0.0002 (11) | −0.0178 (10) |
O1—C2 | 1.238 (2) | C7—H7 | 0.9300 |
O2—C4 | 1.347 (2) | C8—H8 | 0.9300 |
O2—H2 | 0.8200 | C9—C10 | 1.493 (2) |
O3—C6 | 1.362 (2) | C9—H9A | 0.9700 |
O3—C9 | 1.430 (2) | C9—H9B | 0.9700 |
C1—C2 | 1.491 (3) | C10—C15 | 1.377 (3) |
C1—H1A | 0.9600 | C10—C11 | 1.379 (3) |
C1—H1B | 0.9600 | C11—C12 | 1.380 (2) |
C1—H1C | 0.9600 | C11—H11 | 0.9300 |
C2—C3 | 1.460 (3) | C12—C13 | 1.371 (3) |
C3—C4 | 1.400 (3) | C12—H12 | 0.9300 |
C3—C8 | 1.404 (2) | C13—C14 | 1.365 (3) |
C4—C5 | 1.386 (2) | C13—H13 | 0.9300 |
C5—C6 | 1.383 (2) | C14—C15 | 1.383 (3) |
C5—H5 | 0.9300 | C14—H14 | 0.9300 |
C6—C7 | 1.392 (2) | C15—H15 | 0.9300 |
C7—C8 | 1.368 (2) | ||
C4—O2—H2 | 109.5 | C7—C8—H8 | 118.8 |
C6—O3—C9 | 117.04 (14) | C3—C8—H8 | 118.8 |
C2—C1—H1A | 109.5 | O3—C9—C10 | 109.89 (15) |
C2—C1—H1B | 109.5 | O3—C9—H9A | 109.7 |
H1A—C1—H1B | 109.5 | C10—C9—H9A | 109.7 |
C2—C1—H1C | 109.5 | O3—C9—H9B | 109.7 |
H1A—C1—H1C | 109.5 | C10—C9—H9B | 109.7 |
H1B—C1—H1C | 109.5 | H9A—C9—H9B | 108.2 |
O1—C2—C3 | 120.3 (2) | C15—C10—C11 | 118.14 (18) |
O1—C2—C1 | 119.2 (2) | C15—C10—C9 | 120.72 (17) |
C3—C2—C1 | 120.5 (2) | C11—C10—C9 | 121.03 (18) |
C4—C3—C8 | 116.92 (17) | C10—C11—C12 | 121.11 (19) |
C4—C3—C2 | 120.48 (19) | C10—C11—H11 | 119.4 |
C8—C3—C2 | 122.6 (2) | C12—C11—H11 | 119.4 |
O2—C4—C5 | 116.22 (19) | C13—C12—C11 | 119.94 (19) |
O2—C4—C3 | 122.26 (17) | C13—C12—H12 | 120.0 |
C5—C4—C3 | 121.51 (17) | C11—C12—H12 | 120.0 |
C6—C5—C4 | 119.41 (19) | C14—C13—C12 | 119.7 (2) |
C6—C5—H5 | 120.3 | C14—C13—H13 | 120.2 |
C4—C5—H5 | 120.3 | C12—C13—H13 | 120.2 |
O3—C6—C5 | 123.69 (18) | C13—C14—C15 | 120.3 (2) |
O3—C6—C7 | 115.64 (16) | C13—C14—H14 | 119.8 |
C5—C6—C7 | 120.67 (17) | C15—C14—H14 | 119.8 |
C8—C7—C6 | 119.02 (18) | C10—C15—C14 | 120.81 (19) |
C8—C7—H7 | 120.5 | C10—C15—H15 | 119.6 |
C6—C7—H7 | 120.5 | C14—C15—H15 | 119.6 |
C7—C8—C3 | 122.5 (2) | ||
O1—C2—C3—C4 | 1.6 (3) | C5—C6—C7—C8 | −0.3 (3) |
C1—C2—C3—C4 | −179.90 (17) | C6—C7—C8—C3 | 0.5 (3) |
O1—C2—C3—C8 | −177.70 (18) | C4—C3—C8—C7 | −1.0 (3) |
C1—C2—C3—C8 | 0.8 (3) | C2—C3—C8—C7 | 178.29 (16) |
C8—C3—C4—O2 | −179.70 (16) | C6—O3—C9—C10 | 176.25 (14) |
C2—C3—C4—O2 | 1.0 (3) | O3—C9—C10—C15 | 117.1 (2) |
C8—C3—C4—C5 | 1.3 (3) | O3—C9—C10—C11 | −66.5 (2) |
C2—C3—C4—C5 | −178.00 (16) | C15—C10—C11—C12 | 0.9 (3) |
O2—C4—C5—C6 | 179.84 (16) | C9—C10—C11—C12 | −175.56 (18) |
C3—C4—C5—C6 | −1.1 (3) | C10—C11—C12—C13 | 0.0 (3) |
C9—O3—C6—C5 | 1.4 (2) | C11—C12—C13—C14 | −0.6 (3) |
C9—O3—C6—C7 | −178.88 (15) | C12—C13—C14—C15 | 0.3 (3) |
C4—C5—C6—O3 | −179.73 (15) | C11—C10—C15—C14 | −1.2 (3) |
C4—C5—C6—C7 | 0.6 (3) | C9—C10—C15—C14 | 175.30 (19) |
O3—C6—C7—C8 | −179.99 (15) | C13—C14—C15—C10 | 0.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 | 1.84 | 2.554 (2) | 146 |
C1—H1B···O2i | 0.96 | 2.52 | 3.408 (3) | 154 |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C15H14O3 |
Mr | 242.26 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 5.8433 (7), 8.0096 (8), 13.8089 (13) |
α, β, γ (°) | 74.061 (1), 84.589 (1), 87.372 (2) |
V (Å3) | 618.54 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.23 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.980, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3169, 2167, 1291 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.114, 1.02 |
No. of reflections | 2167 |
No. of parameters | 165 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.14 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1 | 0.82 | 1.84 | 2.554 (2) | 146 |
C1—H1B···O2i | 0.96 | 2.52 | 3.408 (3) | 154 |
Symmetry code: (i) x−1, y, z. |
Acknowledgements
We would like to acknowledge funding support by Shaanxi Province Science and Technology (under contract No. 2011 K02–07) and the Program of Northwest A&F University (No. Z111020908).
References
Dermer, O. C. (1934). Chem. Rev. 14, 385–430. CrossRef CAS Google Scholar
Ma, Y.-T., Zhang, A.-L., Yuan, M.-S. & Gao, J.-M. (2010). Acta Cryst. E66, o2468. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mendelson, W. L., Holmes, M. & Dougherty, J. (1996). Synth. Commun. 26, 593–601. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
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The Williamson reaction is a very useful transformation in organic synthesis since the products are of value in both industrial and academic applications. It usually involves the employment of an alkali-metal salt of the hydroxy compound and an alkyl halide (Dermer, 1934). Synthetic procedures to ethers derived from 2,4-dihydroxy-acetophenone as well as the structural characterisation of a related molecule have been described before (Mendelson et al., 1996; Ma et al., 2010).
In this paper, we present the title compound, (I), which was synthesized by the reaction of 2, 4-dihydroxy-acetonephenone, potassium carbonate and benzyl bromide. In (I) (Fig. 1), the dihedral angle between the aromatic rings is 53.48 (4)°. The crystal packing exhibits no significantly short intermolecular contacts.