organic compounds
1-(2-Hydroxy-4,5-dimethoxyphenyl)ethanone
aMolecular Sciences Institute, School of Chemistry, University of the Witwatersrand, PO Wits 2050, Johannesburg, South Africa
*Correspondence e-mail: joseph.michael@wits.ac.za
The molecular structure of the title compound, C10H12O4, contains an intramolecular hydrogen bond between the phenol and acetyl substituents. In the crystal, C—H⋯π interactions act between the molecules in a cyclic manner to stabilize stacks of molecules along the b axis. Several C—H⋯O interactions are present between the stacks.
Related literature
For a review on lamellarin et al. (2008). The experimental procedure of Combes et al. (2002) for a related Fries rearrangement was adapted for the synthesis of the title compound. For alternative syntheses of the title compound by Fries rearrangement, see: Ploypradith et al. (2003); Nolan et al. (2009).
see: FanExperimental
Crystal data
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Data collection
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); data reduction: SAINT; 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, 2012) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812051057/nk2196sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812051057/nk2196Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812051057/nk2196Isup3.cml
The experimental procedure of Combes et al.. (2002) for a related Fries rearrangement was adapted for the synthesis of the title compound. Boron trifloride etherate (20 ml, 23.1 g, 163 mmol) was cautiously added to ice-cooled 3,4-dimethoxyphenyl acetate (7.99 g, 40.7 mmol). The mixture was warmed to room temperature, then heated to 383 K for 5 h before being cooled again to room temperature and stirred for an additional 18 h. Water (50 ml) was added, resulting in the precipitation of a brown solid. This was filtered off, washed with a copious amount of water, then recrystallized from methanol to afford 1-(2-hydroxy-4,5-dimethoxyphenyl)ethanone (4.90 g, 61%) as dark yellow blocks, m.p. 385–386 K.
All H atoms attached to carbon were positioned geometrically, and allowed to ride on their parent atoms, with C—H bond lengths of 0.95 Å (CH) or 0.98 Å (CH3), and isotropic displacement parameters set to 1.2 (CH) or 1.5 times (CH3) the Ueq of the parent atom. Friedel pairs were merged during final refinement.
The title organic compound (Fig. 1), required as an intermediate in the synthesis of lamellarin
(Fan et al., 2008), was prepared by Fries rearrangement of 3,4-dimethoxyphenyl acetate with boron trifluoride etherate. Syntheses of the same compound by related Fries rearrangements have been reported by Ploypradith et al. (2003) and Nolan et al. (2009).The compound crystallizes in the polar π interactions which act between the molecules in a cyclic manner. These stabilize stacks of molecules along the b axis (Fig. 2). Several C—H···O interactions exist in the structure, the most significant being listed in Table 1. These act between the stacks to stabilize the structure (Fig. 3).
Pca21. An intramolecular hydrogen bond exists between the phenol and acetyl groups (Fig. 1). Molecules related by translation along the b axis interact through two C—H···For a review on lamellarin
see: Fan et al. (2008). The experimental procedure of Combes et al.. (2002) for a related Fries rearrangement was adapted for the synthesis of the title compound. For alternative syntheses of the title compound by Fries rearrangement, see: Ploypradith et al. (2003); Nolan et al. (2009).Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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, 2012) and SCHAKAL99 (Keller, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012) and PLATON (Spek, 2009).Fig. 1. The molecular structure of (I), showing the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. C-H···π interactions in the structure of (I) stabilising stacks of molecules along the b axis. [Symmetry codes: (i) x, y, z; (ii) x, -1+y, z; (iii) x, 1+y, z.] | |
Fig. 3. C-H···O interactions between the stacks of molecules in the structure of (I). [Symmetry codes: (i) x, y, z; (ii) 1/2-x, 1+y, 1/2+z; (iii) 1-x, 1-y, 1/2+z; (iv) 1/2+x, -y, z; (v) 1-x, -y, -1/2+z.] |
C10H12O4 | F(000) = 416 |
Mr = 196.20 | Dx = 1.373 Mg m−3 |
Orthorhombic, Pca21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2ac | Cell parameters from 2177 reflections |
a = 19.1740 (12) Å | θ = 3.1–27.7° |
b = 5.5026 (3) Å | µ = 0.11 mm−1 |
c = 8.9956 (5) Å | T = 173 K |
V = 949.10 (9) Å3 | Block, colourless |
Z = 4 | 0.41 × 0.32 × 0.20 mm |
Bruker APEXII CCD diffractometer | 1106 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.032 |
Graphite monochromator | θmax = 28.0°, θmin = 2.1° |
φ and ω scans | h = −25→24 |
4718 measured reflections | k = −7→7 |
1214 independent reflections | l = −11→10 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0504P)2 + 0.0546P] where P = (Fo2 + 2Fc2)/3 |
1214 reflections | (Δ/σ)max < 0.001 |
134 parameters | Δρmax = 0.20 e Å−3 |
1 restraint | Δρmin = −0.18 e Å−3 |
C10H12O4 | V = 949.10 (9) Å3 |
Mr = 196.20 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 19.1740 (12) Å | µ = 0.11 mm−1 |
b = 5.5026 (3) Å | T = 173 K |
c = 8.9956 (5) Å | 0.41 × 0.32 × 0.20 mm |
Bruker APEXII CCD diffractometer | 1106 reflections with I > 2σ(I) |
4718 measured reflections | Rint = 0.032 |
1214 independent reflections |
R[F2 > 2σ(F2)] = 0.032 | 1 restraint |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.20 e Å−3 |
1214 reflections | Δρmin = −0.18 e Å−3 |
134 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 | ||
C1 | 0.34395 (9) | −0.0487 (3) | 0.3973 (2) | 0.0287 (4) | |
C2 | 0.30480 (9) | 0.1288 (3) | 0.4721 (2) | 0.0322 (4) | |
C3 | 0.33683 (9) | 0.2885 (3) | 0.5713 (2) | 0.0307 (4) | |
H3 | 0.3100 | 0.4093 | 0.6205 | 0.037* | |
C4 | 0.40755 (9) | 0.2705 (3) | 0.59765 (19) | 0.0262 (4) | |
C5 | 0.44769 (8) | 0.0884 (3) | 0.5258 (2) | 0.0248 (4) | |
C6 | 0.41609 (9) | −0.0644 (3) | 0.4263 (2) | 0.0271 (4) | |
H6 | 0.4432 | −0.1829 | 0.3758 | 0.033* | |
C7 | 0.30942 (10) | −0.2140 (4) | 0.2923 (2) | 0.0346 (4) | |
C8 | 0.35122 (11) | −0.4047 (4) | 0.2122 (3) | 0.0395 (5) | |
H8A | 0.3210 | −0.4921 | 0.1425 | 0.059* | |
H8B | 0.3706 | −0.5194 | 0.2845 | 0.059* | |
H8C | 0.3893 | −0.3269 | 0.1573 | 0.059* | |
C9 | 0.40535 (10) | 0.5915 (3) | 0.7748 (3) | 0.0357 (4) | |
H9A | 0.3838 | 0.7080 | 0.7064 | 0.053* | |
H9B | 0.4368 | 0.6778 | 0.8426 | 0.053* | |
H9C | 0.3690 | 0.5091 | 0.8323 | 0.053* | |
C10 | 0.55610 (10) | −0.1202 (3) | 0.5150 (3) | 0.0364 (5) | |
H10A | 0.5342 | −0.2712 | 0.5491 | 0.055* | |
H10B | 0.6036 | −0.1097 | 0.5548 | 0.055* | |
H10C | 0.5578 | −0.1188 | 0.4061 | 0.055* | |
O1 | 0.23555 (7) | 0.1547 (3) | 0.4504 (2) | 0.0469 (4) | |
O2 | 0.44429 (7) | 0.4153 (2) | 0.69134 (15) | 0.0308 (3) | |
O3 | 0.51633 (6) | 0.0824 (3) | 0.56605 (17) | 0.0321 (3) | |
O4 | 0.24611 (9) | −0.2002 (3) | 0.2697 (2) | 0.0501 (4) | |
H1 | 0.2231 (13) | 0.032 (5) | 0.385 (4) | 0.061 (8)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0269 (9) | 0.0322 (9) | 0.0270 (9) | −0.0045 (7) | −0.0010 (7) | 0.0009 (8) |
C2 | 0.0227 (8) | 0.0382 (10) | 0.0357 (10) | −0.0005 (8) | 0.0018 (8) | 0.0028 (9) |
C3 | 0.0280 (8) | 0.0334 (9) | 0.0308 (10) | 0.0027 (7) | 0.0050 (8) | 0.0000 (8) |
C4 | 0.0297 (9) | 0.0267 (8) | 0.0222 (8) | −0.0035 (7) | 0.0024 (7) | 0.0010 (7) |
C5 | 0.0214 (8) | 0.0284 (8) | 0.0247 (8) | −0.0017 (7) | 0.0017 (7) | 0.0017 (7) |
C6 | 0.0278 (8) | 0.0279 (8) | 0.0257 (9) | −0.0015 (7) | 0.0036 (7) | −0.0002 (7) |
C7 | 0.0331 (10) | 0.0384 (10) | 0.0322 (10) | −0.0113 (8) | −0.0023 (8) | 0.0015 (9) |
C8 | 0.0439 (12) | 0.0401 (11) | 0.0345 (10) | −0.0141 (9) | 0.0022 (9) | −0.0072 (9) |
C9 | 0.0424 (11) | 0.0304 (9) | 0.0342 (9) | 0.0044 (7) | 0.0023 (9) | −0.0072 (8) |
C10 | 0.0279 (8) | 0.0346 (9) | 0.0468 (12) | 0.0064 (8) | −0.0022 (9) | −0.0067 (9) |
O1 | 0.0229 (7) | 0.0571 (9) | 0.0608 (11) | 0.0031 (7) | −0.0054 (7) | −0.0103 (9) |
O2 | 0.0298 (7) | 0.0323 (6) | 0.0304 (7) | 0.0003 (5) | −0.0003 (5) | −0.0072 (6) |
O3 | 0.0235 (6) | 0.0356 (6) | 0.0371 (7) | 0.0029 (5) | −0.0026 (5) | −0.0097 (6) |
O4 | 0.0327 (7) | 0.0585 (9) | 0.0589 (10) | −0.0089 (7) | −0.0106 (8) | −0.0106 (9) |
C1—C2 | 1.403 (3) | C7—C8 | 1.504 (3) |
C1—C6 | 1.410 (2) | C8—H8A | 0.9800 |
C1—C7 | 1.469 (3) | C8—H8B | 0.9800 |
C2—O1 | 1.349 (2) | C8—H8C | 0.9800 |
C2—C3 | 1.395 (3) | C9—O2 | 1.436 (2) |
C3—C4 | 1.380 (2) | C9—H9A | 0.9800 |
C3—H3 | 0.9500 | C9—H9B | 0.9800 |
C4—O2 | 1.357 (2) | C9—H9C | 0.9800 |
C4—C5 | 1.419 (2) | C10—O3 | 1.426 (2) |
C5—O3 | 1.365 (2) | C10—H10A | 0.9800 |
C5—C6 | 1.370 (2) | C10—H10B | 0.9800 |
C6—H6 | 0.9500 | C10—H10C | 0.9800 |
C7—O4 | 1.233 (2) | O1—H1 | 0.93 (3) |
C2—C1—C6 | 118.60 (16) | C7—C8—H8A | 109.5 |
C2—C1—C7 | 119.87 (16) | C7—C8—H8B | 109.5 |
C6—C1—C7 | 121.53 (16) | H8A—C8—H8B | 109.5 |
O1—C2—C3 | 117.31 (18) | C7—C8—H8C | 109.5 |
O1—C2—C1 | 122.06 (18) | H8A—C8—H8C | 109.5 |
C3—C2—C1 | 120.63 (15) | H8B—C8—H8C | 109.5 |
C4—C3—C2 | 119.84 (16) | O2—C9—H9A | 109.5 |
C4—C3—H3 | 120.1 | O2—C9—H9B | 109.5 |
C2—C3—H3 | 120.1 | H9A—C9—H9B | 109.5 |
O2—C4—C3 | 125.10 (16) | O2—C9—H9C | 109.5 |
O2—C4—C5 | 114.56 (15) | H9A—C9—H9C | 109.5 |
C3—C4—C5 | 120.33 (16) | H9B—C9—H9C | 109.5 |
O3—C5—C6 | 125.79 (15) | O3—C10—H10A | 109.5 |
O3—C5—C4 | 114.79 (15) | O3—C10—H10B | 109.5 |
C6—C5—C4 | 119.42 (15) | H10A—C10—H10B | 109.5 |
C5—C6—C1 | 121.15 (15) | O3—C10—H10C | 109.5 |
C5—C6—H6 | 119.4 | H10A—C10—H10C | 109.5 |
C1—C6—H6 | 119.4 | H10B—C10—H10C | 109.5 |
O4—C7—C1 | 120.76 (19) | C2—O1—H1 | 105.6 (16) |
O4—C7—C8 | 119.24 (18) | C4—O2—C9 | 116.82 (14) |
C1—C7—C8 | 120.00 (17) | C5—O3—C10 | 116.68 (14) |
C6—C1—C2—O1 | −179.90 (19) | O3—C5—C6—C1 | 177.32 (16) |
C7—C1—C2—O1 | −0.3 (3) | C4—C5—C6—C1 | −2.0 (2) |
C6—C1—C2—C3 | 0.9 (3) | C2—C1—C6—C5 | 0.5 (2) |
C7—C1—C2—C3 | −179.47 (17) | C7—C1—C6—C5 | −179.13 (17) |
O1—C2—C3—C4 | −179.95 (18) | C2—C1—C7—O4 | −0.6 (3) |
C1—C2—C3—C4 | −0.7 (3) | C6—C1—C7—O4 | 178.99 (19) |
C2—C3—C4—O2 | 179.97 (17) | C2—C1—C7—C8 | −179.90 (17) |
C2—C3—C4—C5 | −0.8 (3) | C6—C1—C7—C8 | −0.3 (3) |
O2—C4—C5—O3 | 2.1 (2) | C3—C4—O2—C9 | 3.5 (3) |
C3—C4—C5—O3 | −177.21 (16) | C5—C4—O2—C9 | −175.75 (15) |
O2—C4—C5—C6 | −178.53 (15) | C6—C5—O3—C10 | −8.9 (3) |
C3—C4—C5—C6 | 2.2 (2) | C4—C5—O3—C10 | 170.47 (16) |
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4 | 0.93 (3) | 1.71 (3) | 2.549 (2) | 150 (2) |
C8—H8C···O3i | 0.98 | 2.40 | 3.365 (2) | 168 |
C9—H9B···O3ii | 0.98 | 2.57 | 3.513 (3) | 162 |
C10—H10C···O2i | 0.98 | 2.53 | 3.334 (3) | 139 |
C8—H8B···Cg1iii | 0.98 | 2.80 | 3.738 (3) | 160 |
C9—H9A···Cg1iv | 0.98 | 2.90 | 3.828 (3) | 158 |
Symmetry codes: (i) −x+1, −y, z−1/2; (ii) −x+1, −y+1, z+1/2; (iii) x, y−1, z; (iv) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C10H12O4 |
Mr | 196.20 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 173 |
a, b, c (Å) | 19.1740 (12), 5.5026 (3), 8.9956 (5) |
V (Å3) | 949.10 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.11 |
Crystal size (mm) | 0.41 × 0.32 × 0.20 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4718, 1214, 1106 |
Rint | 0.032 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.085, 1.06 |
No. of reflections | 1214 |
No. of parameters | 134 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.18 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and SCHAKAL99 (Keller, 1999), WinGX (Farrugia, 2012) and PLATON (Spek, 2009).
Cg1 is the centroid of the C1–C6 ring. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O4 | 0.93 (3) | 1.71 (3) | 2.549 (2) | 150 (2) |
C8—H8C···O3i | 0.98 | 2.40 | 3.365 (2) | 168 |
C9—H9B···O3ii | 0.98 | 2.57 | 3.513 (3) | 162 |
C10—H10C···O2i | 0.98 | 2.53 | 3.334 (3) | 139 |
C8—H8B···Cg1iii | 0.98 | 2.80 | 3.738 (3) | 160 |
C9—H9A···Cg1iv | 0.98 | 2.90 | 3.828 (3) | 158 |
Symmetry codes: (i) −x+1, −y, z−1/2; (ii) −x+1, −y+1, z+1/2; (iii) x, y−1, z; (iv) x, y+1, z. |
Acknowledgements
This work was supported by the University of the Witwatersrand and the National Research Foundation, Pretoria (grant No. 78837).
References
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The title organic compound (Fig. 1), required as an intermediate in the synthesis of lamellarin alkaloids (Fan et al., 2008), was prepared by Fries rearrangement of 3,4-dimethoxyphenyl acetate with boron trifluoride etherate. Syntheses of the same compound by related Fries rearrangements have been reported by Ploypradith et al. (2003) and Nolan et al. (2009).
The compound crystallizes in the polar space group Pca21. An intramolecular hydrogen bond exists between the phenol and acetyl groups (Fig. 1). Molecules related by translation along the b axis interact through two C—H···π interactions which act between the molecules in a cyclic manner. These stabilize stacks of molecules along the b axis (Fig. 2). Several C—H···O interactions exist in the structure, the most significant being listed in Table 1. These act between the stacks to stabilize the structure (Fig. 3).