organic compounds
3-(4-Methoxyphenyl)-6,7-dihydro-1H-furo[3,4-c]pyran-4(3H)-one
aDepartment of Pharmacy, General Hospital of Shenyang Military Command, Shenyang 110016, People's Republic of China, and bDepartment of Medicinal Chemistry, School of Pharmacy, Second Military Medical University, Shanghai 200433, People's Republic of China
*Correspondence e-mail: hu829Zh213@yahoo.com.cn, sgsgb@126.com
In the title compound, C14H14O4, the dihedral angle between the hydrofuran and benzene rings is 88.41 (15)°. The hydropyran ring adopts an with the O-bound methylene C atom as the flap. In the crystal, weak aromatic π–π stacking is observed [centroid–centroid separation = 3.848 (2) Å].
Experimental
Crystal data
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); 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
10.1107/S160053681204723X/hb6991sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Supporting information file. DOI: 10.1107/S160053681204723X/hb6991Isup2.cdx
Supporting information file. DOI: 10.1107/S160053681204723X/hb6991Isup6.cdx
Structure factors: contains datablock I. DOI: 10.1107/S160053681204723X/hb6991Isup4.hkl
NaH (60% in mineral oil, 24 mmol) was added to a solution of but-2-yne-1,4-diol (2.58 g, 30 mmol) in THF (50 ml) under nitrogen, and the solution was stirred for 5 min at 20 C. Diethyl 2-(4-methoxybenzylidene)malonate (5.56 g, 20 mmol) and CuI (0.38 g, 2 mmol) were then added successively. When consumption of the starting materials was observed by TLC, the reaction mixture was added 3% HCl solution until the PH value was 7. Then the mixture was extracted with CH2Cl2 (30 ml × 3). The combined organic layers were dried and solids were combined. The solid (0.973 g, 3 mmol) subsequently was reacted with 20% KOH in EtOH/THF (15/15 ml) at room temperature for 6 h. Then the reaction mixture was diluted with CH2Cl2 (30 ml) and washed with saturated Na2CO3, brine and dried with MgSO4. The mixture was purified with silica gel column chromagraphy. The Trans-form compounds could be obtained. Yield: 10%. M. p.: 407 K.
All hydrogen atoms were placed in calculated positions using a riding model, with d (C—H) = 0.93 Å for aromatic, 0.97 Å for CH2 and 0.96 Å for CH3 groups, and with Uiso (H) = 1.2 Ueq(C).
Data collection: SMART (Bruker, 2002); cell
SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. The molecular structure of the title compound, with 30% probability displacement ellipsoids for non-H atoms. | |
Fig. 2. A view of the unit-cell contents for the title compound. |
C14H14O4 | F(000) = 520 |
Mr = 246.25 | Dx = 1.350 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 735 reflections |
a = 7.240 (3) Å | θ = 2.6–24.3° |
b = 8.635 (4) Å | µ = 0.10 mm−1 |
c = 19.545 (8) Å | T = 293 K |
β = 97.352 (6)° | Prism, colorless |
V = 1212.0 (9) Å3 | 0.25 × 0.25 × 0.20 mm |
Z = 4 |
Bruker SMART CCD diffractometer | 2127 independent reflections |
Radiation source: fine-focus sealed tube | 1494 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.104 |
phi and ω scans | θmax = 25.0°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | h = −8→7 |
Tmin = 0.976, Tmax = 0.981 | k = −10→10 |
4872 measured reflections | l = −23→19 |
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)] = 0.074 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.227 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1396P)2] where P = (Fo2 + 2Fc2)/3 |
2127 reflections | (Δ/σ)max = 0.001 |
164 parameters | Δρmax = 0.55 e Å−3 |
6 restraints | Δρmin = −0.31 e Å−3 |
C14H14O4 | V = 1212.0 (9) Å3 |
Mr = 246.25 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.240 (3) Å | µ = 0.10 mm−1 |
b = 8.635 (4) Å | T = 293 K |
c = 19.545 (8) Å | 0.25 × 0.25 × 0.20 mm |
β = 97.352 (6)° |
Bruker SMART CCD diffractometer | 2127 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2002) | 1494 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.981 | Rint = 0.104 |
4872 measured reflections |
R[F2 > 2σ(F2)] = 0.074 | 6 restraints |
wR(F2) = 0.227 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.55 e Å−3 |
2127 reflections | Δρmin = −0.31 e Å−3 |
164 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 | 0.3995 (3) | 0.6361 (2) | 0.04179 (10) | 0.0677 (6) | |
O2 | 0.5812 (3) | 0.8161 (3) | 0.00885 (11) | 0.0771 (7) | |
O3 | 0.9242 (3) | 0.4487 (2) | 0.14388 (12) | 0.0777 (7) | |
O4 | 0.2905 (3) | 0.5087 (3) | 0.33985 (12) | 0.0800 (7) | |
C1 | 0.5550 (4) | 0.6850 (3) | 0.04378 (13) | 0.0541 (7) | |
C2 | 0.7206 (3) | 0.6116 (3) | 0.07879 (13) | 0.0542 (7) | |
C3 | 0.7270 (3) | 0.4668 (3) | 0.12146 (15) | 0.0569 (7) | |
H3 | 0.6841 | 0.3796 | 0.0915 | 0.068* | |
C4 | 1.0291 (4) | 0.5583 (4) | 0.1116 (2) | 0.0805 (10) | |
H4A | 1.1033 | 0.5076 | 0.0803 | 0.097* | |
H4B | 1.1116 | 0.6153 | 0.1457 | 0.097* | |
C5 | 0.8909 (4) | 0.6629 (3) | 0.07366 (15) | 0.0622 (8) | |
C6 | 0.9218 (4) | 0.8021 (4) | 0.03314 (19) | 0.0838 (10) | |
H6A | 1.0260 | 0.8605 | 0.0563 | 0.101* | |
H6B | 0.9517 | 0.7719 | −0.0120 | 0.101* | |
C7 | 0.7547 (6) | 0.8987 (5) | 0.0253 (3) | 0.1143 (15) | |
H7A | 0.7502 | 0.9555 | 0.0679 | 0.137* | |
H7B | 0.7654 | 0.9740 | −0.0108 | 0.137* | |
C8 | 0.6177 (3) | 0.4702 (3) | 0.18107 (14) | 0.0525 (7) | |
C9 | 0.4688 (4) | 0.3726 (3) | 0.18314 (15) | 0.0593 (7) | |
H9 | 0.4417 | 0.2997 | 0.1483 | 0.071* | |
C10 | 0.3579 (4) | 0.3798 (3) | 0.23563 (16) | 0.0646 (8) | |
H10 | 0.2584 | 0.3119 | 0.2360 | 0.077* | |
C11 | 0.3952 (4) | 0.4871 (3) | 0.28691 (15) | 0.0593 (7) | |
C12 | 0.5476 (4) | 0.5848 (3) | 0.28669 (16) | 0.0657 (8) | |
H12 | 0.5769 | 0.6556 | 0.3223 | 0.079* | |
C13 | 0.6550 (4) | 0.5765 (3) | 0.23382 (15) | 0.0613 (8) | |
H13 | 0.7550 | 0.6439 | 0.2335 | 0.074* | |
C14 | 0.1150 (5) | 0.4338 (5) | 0.33449 (19) | 0.0881 (11) | |
H14A | 0.0466 | 0.4550 | 0.2901 | 0.132* | |
H14B | 0.0464 | 0.4716 | 0.3699 | 0.132* | |
H14C | 0.1330 | 0.3241 | 0.3398 | 0.132* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0474 (11) | 0.0838 (13) | 0.0720 (13) | 0.0007 (9) | 0.0075 (9) | −0.0005 (10) |
O2 | 0.0686 (13) | 0.0824 (14) | 0.0777 (14) | −0.0039 (10) | −0.0007 (11) | 0.0275 (11) |
O3 | 0.0481 (11) | 0.0835 (13) | 0.1019 (17) | 0.0080 (9) | 0.0110 (11) | 0.0278 (12) |
O4 | 0.0760 (15) | 0.0989 (16) | 0.0681 (14) | −0.0059 (12) | 0.0208 (11) | 0.0058 (11) |
C1 | 0.0532 (16) | 0.0636 (15) | 0.0458 (14) | −0.0009 (12) | 0.0077 (11) | −0.0025 (12) |
C2 | 0.0493 (14) | 0.0612 (14) | 0.0532 (15) | −0.0073 (11) | 0.0109 (12) | −0.0019 (12) |
C3 | 0.0467 (14) | 0.0597 (14) | 0.0643 (16) | −0.0031 (11) | 0.0076 (12) | 0.0027 (13) |
C4 | 0.0480 (16) | 0.091 (2) | 0.103 (2) | −0.0051 (14) | 0.0124 (16) | 0.0236 (19) |
C5 | 0.0490 (15) | 0.0732 (17) | 0.0647 (17) | −0.0080 (12) | 0.0085 (12) | 0.0031 (14) |
C6 | 0.067 (2) | 0.098 (2) | 0.086 (2) | −0.0250 (17) | 0.0082 (17) | 0.0274 (19) |
C7 | 0.092 (3) | 0.104 (3) | 0.144 (4) | −0.017 (2) | 0.006 (3) | 0.053 (3) |
C8 | 0.0444 (14) | 0.0499 (12) | 0.0615 (16) | −0.0012 (10) | 0.0007 (12) | 0.0103 (12) |
C9 | 0.0571 (16) | 0.0583 (14) | 0.0620 (16) | −0.0110 (12) | 0.0051 (13) | 0.0006 (13) |
C10 | 0.0543 (15) | 0.0695 (16) | 0.0691 (18) | −0.0151 (13) | 0.0048 (13) | 0.0096 (15) |
C11 | 0.0540 (16) | 0.0656 (15) | 0.0590 (17) | 0.0025 (12) | 0.0095 (13) | 0.0131 (13) |
C12 | 0.0650 (17) | 0.0652 (16) | 0.0653 (17) | −0.0068 (13) | 0.0018 (14) | −0.0034 (14) |
C13 | 0.0507 (15) | 0.0629 (15) | 0.0696 (18) | −0.0127 (12) | 0.0058 (13) | 0.0028 (14) |
C14 | 0.068 (2) | 0.114 (3) | 0.087 (2) | −0.0002 (18) | 0.0279 (18) | 0.022 (2) |
O1—C1 | 1.198 (3) | C6—H6A | 0.9700 |
O2—C1 | 1.348 (3) | C6—H6B | 0.9700 |
O2—C7 | 1.445 (4) | C7—H7A | 0.9700 |
O3—C4 | 1.411 (4) | C7—H7B | 0.9700 |
O3—C3 | 1.447 (3) | C8—C9 | 1.374 (4) |
O4—C11 | 1.371 (4) | C8—C13 | 1.381 (4) |
O4—C14 | 1.418 (4) | C9—C10 | 1.383 (4) |
C1—C2 | 1.448 (4) | C9—H9 | 0.9300 |
C2—C5 | 1.326 (4) | C10—C11 | 1.366 (4) |
C2—C3 | 1.501 (4) | C10—H10 | 0.9300 |
C3—C8 | 1.490 (4) | C11—C12 | 1.390 (4) |
C3—H3 | 0.9800 | C12—C13 | 1.372 (4) |
C4—C5 | 1.476 (4) | C12—H12 | 0.9300 |
C4—H4A | 0.9700 | C13—H13 | 0.9300 |
C4—H4B | 0.9700 | C14—H14A | 0.9600 |
C5—C6 | 1.472 (4) | C14—H14B | 0.9600 |
C6—C7 | 1.461 (5) | C14—H14C | 0.9600 |
C1—O2—C7 | 118.5 (2) | O2—C7—C6 | 115.2 (3) |
C4—O3—C3 | 111.1 (2) | O2—C7—H7A | 108.5 |
C11—O4—C14 | 117.3 (3) | C6—C7—H7A | 108.5 |
O1—C1—O2 | 118.2 (2) | O2—C7—H7B | 108.5 |
O1—C1—C2 | 125.4 (3) | C6—C7—H7B | 108.5 |
O2—C1—C2 | 116.4 (2) | H7A—C7—H7B | 107.5 |
C5—C2—C1 | 122.7 (3) | C9—C8—C13 | 117.7 (3) |
C5—C2—C3 | 111.0 (2) | C9—C8—C3 | 120.6 (2) |
C1—C2—C3 | 126.3 (2) | C13—C8—C3 | 121.6 (2) |
O3—C3—C8 | 111.6 (2) | C8—C9—C10 | 121.8 (3) |
O3—C3—C2 | 102.55 (19) | C8—C9—H9 | 119.1 |
C8—C3—C2 | 115.9 (2) | C10—C9—H9 | 119.1 |
O3—C3—H3 | 108.9 | C11—C10—C9 | 119.7 (3) |
C8—C3—H3 | 108.9 | C11—C10—H10 | 120.1 |
C2—C3—H3 | 108.9 | C9—C10—H10 | 120.1 |
O3—C4—C5 | 105.4 (2) | C10—C11—O4 | 124.7 (3) |
O3—C4—H4A | 110.7 | C10—C11—C12 | 119.4 (3) |
C5—C4—H4A | 110.7 | O4—C11—C12 | 115.9 (3) |
O3—C4—H4B | 110.7 | C13—C12—C11 | 119.8 (3) |
C5—C4—H4B | 110.7 | C13—C12—H12 | 120.1 |
H4A—C4—H4B | 108.8 | C11—C12—H12 | 120.1 |
C2—C5—C6 | 121.4 (3) | C12—C13—C8 | 121.5 (3) |
C2—C5—C4 | 109.5 (3) | C12—C13—H13 | 119.3 |
C6—C5—C4 | 129.1 (2) | C8—C13—H13 | 119.3 |
C7—C6—C5 | 110.0 (3) | O4—C14—H14A | 109.5 |
C7—C6—H6A | 109.7 | O4—C14—H14B | 109.5 |
C5—C6—H6A | 109.7 | H14A—C14—H14B | 109.5 |
C7—C6—H6B | 109.7 | O4—C14—H14C | 109.5 |
C5—C6—H6B | 109.7 | H14A—C14—H14C | 109.5 |
H6A—C6—H6B | 108.2 | H14B—C14—H14C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C14H14O4 |
Mr | 246.25 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 7.240 (3), 8.635 (4), 19.545 (8) |
β (°) | 97.352 (6) |
V (Å3) | 1212.0 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.25 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
Tmin, Tmax | 0.976, 0.981 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4872, 2127, 1494 |
Rint | 0.104 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.074, 0.227, 1.06 |
No. of reflections | 2127 |
No. of parameters | 164 |
No. of restraints | 6 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.55, −0.31 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
References
Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, T. T., Liu, J., Zhong, H. Y., Chen, H., Lv, Z. L., Zhang, Y. K., Zhang, M. F., Geng, D. P., Niu, C. J., Li, Y. M. & Li, K. (2011). Bioorg. Med. Chem. Lett. 21, 3381–3383. Web of Science CSD CrossRef CAS PubMed Google Scholar
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