organic compounds
Ethyl 4-(2-furyl)-2-oxochroman-3-carboxylate
aInstitute of Life Sciences, University of Hyderabad Campus, Hyderabad 500 046, India
*Correspondence e-mail: anandsolomonk@ilsresearch.org
The title compound, C16H14O5, was prepared from the reaction of 3-carbethoxycoumarin with furan in the presence of AlCl3 as catalyst. In the crystal, intermolecular C—H⋯O hydrogen-bonding interactions between four molecules lead to a tetramer in the The furan ring is antiperiplanar [C—C—C—O = 167.9 (13)°] and the ethoxycarbonyl group is (−)anticlinal [C—C—C—O = −128.6 (14)°] to the lactone ring.
Related literature
For the medicinal and biological activity of et al. (2005); Kontogiorgis & Hadjipavlou-Litina (2005); Gursoy & Karali (2003); Prabhakar et al. (2010). For the assignment of conformations and the orientation of the substituents, see: Nardelli (1983, 1995); Klyne & Prelog (1960).
and their derivatives, see: BorgesExperimental
Crystal data
|
Refinement
|
Data collection: SMART (Bruker, 2003); cell SAINT (Bruker, 2003); 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/S1600536810016193/ds2028sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810016193/ds2028Isup2.hkl
3-Carbethoxy coumarin (3 m mol) was taken into 30 mmol of furan and 10 mol% of AlCl3 catalyst was added. The reaction mixture was stirred at room temperature for 24 hours. After completion of the reaction, the excess of the furan was distilled off and extracted thrice with water/dichloromethane. The product was separated from flash
and recrystallized from dichloromethane.All H atoms were found on difference maps, with C—H=0.93 Å and included in the final cycles of
using a riding model, with Uiso(H)=1.2Ueq(C)We have synthesized and reported our serendipitous observations on the Diels-Alder reaction of 3-carbethoxy coumarin with furan, followed by a ring opening to yield Michael product, 3-carbethoxy-4-(2-furyl)-chroman-2-one in good yields.
For the medicinal and biological activity of
and their derivatives, see: Borges et al. (2005); Kontogiorgis & Hadjipavlou-Litina (2005); Gursoy & Karali (2003); Prabhakar et al. (2010). For the assignment of conformations and the orientation of the substituents, see: Nardelli (1983, 1995); Klyne & Prelog (1960).Data collection: SMART (Bruker, 2003); cell
SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); 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. Chemical diagram of the title compound. | |
Fig. 2. ORTEP diagram of the 3-carbethoxy-4-(2-furyl)-chroman-2-one. (Thermal ellipsoids are at 50% probability level). | |
Fig. 3. Crystal packing of (I) showing the formation of tetramer. The C—H•••O contacts are shown as dashed lines. Symmetry code: (i) 1-x,-1/2+y, 1/2-z (ii) x, -1/2-y, -1/2+z | |
Fig. 4. The formation of the title compound. |
C16H14O5 | F(000) = 600 |
Mr = 286.27 | Dx = 1.373 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 5174 reflections |
a = 10.393 (3) Å | θ = 2.5–25.8° |
b = 8.459 (3) Å | µ = 0.10 mm−1 |
c = 15.819 (5) Å | T = 298 K |
β = 95.464 (5)° | Block, colourless |
V = 1384.5 (8) Å3 | 0.34 × 0.24 × 0.20 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2711 independent reflections |
Radiation source: fine-focus sealed tube | 2099 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
phi and ω scans | θmax = 25.9°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −12→12 |
Tmin = 0.966, Tmax = 0.980 | k = −10→10 |
13767 measured reflections | l = −19→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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.058P)2 + 0.1619P] where P = (Fo2 + 2Fc2)/3 |
2711 reflections | (Δ/σ)max < 0.001 |
227 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.16 e Å−3 |
C16H14O5 | V = 1384.5 (8) Å3 |
Mr = 286.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.393 (3) Å | µ = 0.10 mm−1 |
b = 8.459 (3) Å | T = 298 K |
c = 15.819 (5) Å | 0.34 × 0.24 × 0.20 mm |
β = 95.464 (5)° |
Bruker SMART CCD area-detector diffractometer | 2711 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 2099 reflections with I > 2σ(I) |
Tmin = 0.966, Tmax = 0.980 | Rint = 0.035 |
13767 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.111 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.18 e Å−3 |
2711 reflections | Δρmin = −0.16 e Å−3 |
227 parameters |
x | y | z | Uiso*/Ueq | ||
H2 | 0.5893 (16) | 0.9788 (19) | 0.7769 (10) | 0.045 (4)* | |
H13 | 0.648 (2) | 1.325 (3) | 1.0884 (14) | 0.084 (7)* | |
H11 | 0.598 (2) | 1.251 (2) | 0.8313 (14) | 0.076 (6)* | |
H12 | 0.598 (2) | 1.472 (3) | 0.9435 (13) | 0.081 (6)* | |
H7 | 1.082 (2) | 0.672 (3) | 1.0318 (14) | 0.085 (7)* | |
H6 | 0.8933 (19) | 0.630 (2) | 1.0962 (13) | 0.073 (6)* | |
H8 | 1.077 (2) | 0.828 (2) | 0.9093 (13) | 0.078 (6)* | |
H5 | 0.6973 (18) | 0.7462 (19) | 1.0400 (11) | 0.048 (5)* | |
H3 | 0.5753 (15) | 0.8783 (17) | 0.9186 (9) | 0.033 (4)* | |
C6 | 0.8921 (2) | 0.6956 (2) | 1.04771 (12) | 0.0626 (5) | |
O3 | 0.65502 (12) | 1.13244 (14) | 1.01627 (7) | 0.0545 (3) | |
O1 | 0.88812 (11) | 0.98037 (14) | 0.83531 (7) | 0.0523 (3) | |
O5 | 0.74734 (13) | 0.71312 (14) | 0.73664 (7) | 0.0598 (4) | |
O2 | 0.78518 (13) | 1.08381 (15) | 0.72090 (7) | 0.0635 (4) | |
C3 | 0.65067 (15) | 0.93666 (18) | 0.90397 (9) | 0.0404 (4) | |
O4 | 0.57089 (13) | 0.66307 (15) | 0.80304 (8) | 0.0651 (4) | |
C4 | 0.77275 (15) | 0.86004 (17) | 0.94453 (9) | 0.0388 (4) | |
C1 | 0.77894 (17) | 1.00313 (19) | 0.78254 (10) | 0.0460 (4) | |
C9 | 0.88546 (15) | 0.88312 (18) | 0.90688 (10) | 0.0429 (4) | |
C2 | 0.65772 (16) | 0.92533 (19) | 0.80739 (10) | 0.0425 (4) | |
C14 | 0.65204 (17) | 0.7516 (2) | 0.78227 (10) | 0.0465 (4) | |
C13 | 0.63873 (19) | 1.2923 (2) | 1.02691 (14) | 0.0597 (5) | |
C8 | 1.00056 (18) | 0.8154 (2) | 0.93811 (12) | 0.0576 (5) | |
C5 | 0.77720 (19) | 0.7640 (2) | 1.01532 (10) | 0.0502 (4) | |
C10 | 0.63742 (14) | 1.10518 (19) | 0.93083 (9) | 0.0419 (4) | |
C11 | 0.61161 (18) | 1.2410 (2) | 0.89003 (12) | 0.0550 (5) | |
C12 | 0.61250 (19) | 1.3618 (2) | 0.95281 (13) | 0.0593 (5) | |
C15 | 0.7673 (2) | 0.5456 (2) | 0.71929 (12) | 0.0718 (6) | |
H15A | 0.8029 | 0.5339 | 0.6652 | 0.086* | |
H15B | 0.6853 | 0.4902 | 0.7162 | 0.086* | |
C7 | 1.0035 (2) | 0.7225 (2) | 1.00924 (13) | 0.0656 (5) | |
C16 | 0.8571 (2) | 0.4771 (2) | 0.78765 (14) | 0.0738 (6) | |
H16A | 0.9356 | 0.5376 | 0.7935 | 0.111* | |
H16B | 0.8763 | 0.3698 | 0.7737 | 0.111* | |
H16C | 0.8177 | 0.4795 | 0.8401 | 0.111* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C6 | 0.0812 (15) | 0.0569 (11) | 0.0475 (10) | 0.0109 (10) | −0.0047 (10) | 0.0124 (9) |
O3 | 0.0658 (8) | 0.0534 (7) | 0.0449 (7) | 0.0049 (6) | 0.0093 (5) | −0.0084 (5) |
O1 | 0.0463 (7) | 0.0581 (7) | 0.0526 (7) | −0.0034 (5) | 0.0059 (5) | 0.0137 (6) |
O5 | 0.0819 (9) | 0.0466 (7) | 0.0524 (7) | 0.0094 (6) | 0.0151 (7) | −0.0060 (5) |
O2 | 0.0824 (9) | 0.0614 (8) | 0.0474 (7) | 0.0061 (7) | 0.0110 (6) | 0.0171 (6) |
C3 | 0.0377 (8) | 0.0423 (9) | 0.0416 (8) | −0.0022 (7) | 0.0052 (7) | −0.0030 (7) |
O4 | 0.0666 (8) | 0.0592 (8) | 0.0684 (9) | −0.0165 (7) | 0.0007 (7) | −0.0116 (6) |
C4 | 0.0459 (9) | 0.0342 (8) | 0.0357 (8) | −0.0005 (6) | 0.0000 (6) | −0.0043 (6) |
C1 | 0.0571 (10) | 0.0409 (9) | 0.0403 (9) | 0.0072 (7) | 0.0058 (8) | 0.0004 (7) |
C9 | 0.0453 (9) | 0.0417 (8) | 0.0410 (8) | −0.0012 (7) | 0.0005 (7) | 0.0016 (7) |
C2 | 0.0446 (9) | 0.0423 (9) | 0.0392 (8) | 0.0078 (7) | −0.0041 (7) | −0.0021 (7) |
C14 | 0.0539 (10) | 0.0482 (9) | 0.0352 (8) | 0.0012 (8) | −0.0077 (7) | −0.0034 (7) |
C13 | 0.0629 (12) | 0.0556 (11) | 0.0622 (12) | −0.0001 (9) | 0.0144 (10) | −0.0197 (10) |
C8 | 0.0456 (10) | 0.0652 (12) | 0.0609 (11) | 0.0047 (8) | −0.0008 (9) | 0.0030 (9) |
C5 | 0.0623 (11) | 0.0471 (10) | 0.0420 (9) | −0.0002 (8) | 0.0081 (8) | 0.0010 (8) |
C10 | 0.0384 (8) | 0.0479 (9) | 0.0394 (8) | 0.0024 (7) | 0.0044 (6) | −0.0057 (7) |
C11 | 0.0628 (12) | 0.0512 (10) | 0.0508 (11) | 0.0106 (8) | 0.0039 (9) | −0.0008 (9) |
C12 | 0.0629 (12) | 0.0441 (10) | 0.0723 (13) | 0.0059 (9) | 0.0138 (10) | −0.0066 (9) |
C15 | 0.1093 (17) | 0.0474 (11) | 0.0597 (12) | 0.0141 (11) | 0.0133 (12) | −0.0108 (9) |
C7 | 0.0622 (13) | 0.0673 (13) | 0.0641 (12) | 0.0171 (10) | −0.0104 (10) | 0.0071 (10) |
C16 | 0.0813 (15) | 0.0552 (11) | 0.0863 (15) | 0.0111 (10) | 0.0158 (12) | 0.0064 (11) |
C6—C7 | 1.377 (3) | C2—C14 | 1.522 (2) |
C6—C5 | 1.381 (3) | C2—H2 | 0.937 (17) |
C6—H6 | 0.94 (2) | C13—C12 | 1.317 (3) |
O3—C10 | 1.3663 (19) | C13—H13 | 1.01 (2) |
O3—C13 | 1.375 (2) | C8—C7 | 1.371 (3) |
O1—C1 | 1.357 (2) | C8—H8 | 0.96 (2) |
O1—C9 | 1.4020 (19) | C5—H5 | 0.962 (18) |
O5—C14 | 1.321 (2) | C10—C11 | 1.333 (2) |
O5—C15 | 1.462 (2) | C11—C12 | 1.425 (3) |
O2—C1 | 1.1969 (19) | C11—H11 | 0.93 (2) |
C3—C10 | 1.498 (2) | C12—H12 | 0.95 (2) |
C3—C4 | 1.512 (2) | C15—C16 | 1.478 (3) |
C3—C2 | 1.539 (2) | C15—H15A | 0.9700 |
C3—H3 | 0.972 (15) | C15—H15B | 0.9700 |
O4—C14 | 1.197 (2) | C7—H7 | 0.95 (2) |
C4—C9 | 1.378 (2) | C16—H16A | 0.9600 |
C4—C5 | 1.381 (2) | C16—H16B | 0.9600 |
C1—C2 | 1.506 (2) | C16—H16C | 0.9600 |
C9—C8 | 1.375 (2) | ||
C7—C6—C5 | 120.05 (18) | O3—C13—H13 | 113.0 (13) |
C7—C6—H6 | 120.5 (13) | C7—C8—C9 | 118.97 (19) |
C5—C6—H6 | 119.4 (13) | C7—C8—H8 | 119.9 (13) |
C10—O3—C13 | 106.29 (14) | C9—C8—H8 | 121.0 (13) |
C1—O1—C9 | 120.03 (12) | C6—C5—C4 | 120.55 (18) |
C14—O5—C15 | 117.97 (15) | C6—C5—H5 | 122.2 (10) |
C10—C3—C4 | 112.56 (13) | C4—C5—H5 | 117.2 (10) |
C10—C3—C2 | 110.80 (13) | C11—C10—O3 | 109.59 (14) |
C4—C3—C2 | 106.09 (12) | C11—C10—C3 | 134.68 (15) |
C10—C3—H3 | 108.5 (8) | O3—C10—C3 | 115.73 (13) |
C4—C3—H3 | 110.1 (8) | C10—C11—C12 | 107.06 (17) |
C2—C3—H3 | 108.7 (8) | C10—C11—H11 | 124.6 (13) |
C9—C4—C5 | 118.03 (15) | C12—C11—H11 | 128.3 (13) |
C9—C4—C3 | 117.99 (13) | C13—C12—C11 | 106.68 (17) |
C5—C4—C3 | 123.94 (15) | C13—C12—H12 | 126.2 (13) |
O2—C1—O1 | 118.36 (16) | C11—C12—H12 | 127.1 (13) |
O2—C1—C2 | 124.98 (16) | O5—C15—C16 | 109.51 (16) |
O1—C1—C2 | 116.65 (13) | O5—C15—H15A | 109.8 |
C8—C9—C4 | 122.14 (15) | C16—C15—H15A | 109.8 |
C8—C9—O1 | 116.82 (15) | O5—C15—H15B | 109.8 |
C4—C9—O1 | 121.02 (13) | C16—C15—H15B | 109.8 |
C1—C2—C14 | 111.48 (13) | H15A—C15—H15B | 108.2 |
C1—C2—C3 | 110.60 (13) | C8—C7—C6 | 120.24 (18) |
C14—C2—C3 | 108.36 (13) | C8—C7—H7 | 120.9 (14) |
C1—C2—H2 | 105.5 (10) | C6—C7—H7 | 118.8 (14) |
C14—C2—H2 | 108.9 (10) | C15—C16—H16A | 109.5 |
C3—C2—H2 | 112.1 (10) | C15—C16—H16B | 109.5 |
O4—C14—O5 | 125.46 (16) | H16A—C16—H16B | 109.5 |
O4—C14—C2 | 122.91 (16) | C15—C16—H16C | 109.5 |
O5—C14—C2 | 111.62 (15) | H16A—C16—H16C | 109.5 |
C12—C13—O3 | 110.37 (17) | H16B—C16—H16C | 109.5 |
C12—C13—H13 | 136.6 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O3i | 0.972 (15) | 2.696 (15) | 3.576 (2) | 150.8 (11) |
C16—H16B···O2ii | 0.96 | 2.70 | 3.549 (3) | 148 |
C16—H16A···O2iii | 0.96 | 2.96 | 3.841 (3) | 153 |
C8—H8···O3iv | 0.96 (2) | 2.94 (2) | 3.611 (3) | 128.2 (15) |
C11—H11···O4v | 0.93 (2) | 2.73 (2) | 3.501 (3) | 140.9 (17) |
C13—H13···O2vi | 1.01 (2) | 2.54 (2) | 3.456 (3) | 151.0 (17) |
C12—H12···O4vii | 0.95 (2) | 2.74 (2) | 3.478 (3) | 134.9 (16) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) x, y−1, z; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, −y+2, −z+2; (v) −x+1, y+1/2, −z+3/2; (vi) x, −y+5/2, z+1/2; (vii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C16H14O5 |
Mr | 286.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.393 (3), 8.459 (3), 15.819 (5) |
β (°) | 95.464 (5) |
V (Å3) | 1384.5 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.34 × 0.24 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.966, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13767, 2711, 2099 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.615 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.111, 1.04 |
No. of reflections | 2711 |
No. of parameters | 227 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.16 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O3i | 0.972 (15) | 2.696 (15) | 3.576 (2) | 150.8 (11) |
C16—H16B···O2ii | 0.96 | 2.70 | 3.549 (3) | 147.6 |
C16—H16A···O2iii | 0.96 | 2.96 | 3.841 (3) | 153.4 |
C8—H8···O3iv | 0.96 (2) | 2.94 (2) | 3.611 (3) | 128.2 (15) |
C11—H11···O4v | 0.93 (2) | 2.73 (2) | 3.501 (3) | 140.9 (17) |
C13—H13···O2vi | 1.01 (2) | 2.54 (2) | 3.456 (3) | 151.0 (17) |
C12—H12···O4vii | 0.95 (2) | 2.74 (2) | 3.478 (3) | 134.9 (16) |
Symmetry codes: (i) −x+1, −y+2, −z+2; (ii) x, y−1, z; (iii) −x+2, y−1/2, −z+3/2; (iv) −x+2, −y+2, −z+2; (v) −x+1, y+1/2, −z+3/2; (vi) x, −y+5/2, z+1/2; (vii) x, y+1, z. |
Acknowledgements
We thank the Director, Institute of Life Sciences, for support and also the Dean, School of Chemistry, University of Hyderabad, for the X-ray crystallographic data.
References
Borges, F., Roleira, F., Milhazes, N., Santana, L. & Uriarte, E. (2005). Curr. Med. Chem. 12, 887–916. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (2003). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Gursoy, A. & &Karali, N. (2003). Turk. J. Chem. 27, 545–551. Google Scholar
Klyne, W. & Prelog, V. (1960). Experientia, 16, 521–568. CrossRef CAS Web of Science Google Scholar
Kontogiorgis, C. A. & Hadjipavlou-Litina, D. J. (2005). J. Med. Chem. 48, 6400–6408. Web of Science CrossRef PubMed CAS Google Scholar
Nardelli, M. (1983). Acta Cryst. C39, 1141–1142. CrossRef CAS Web of Science IUCr Journals Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Prabhakar, M., Narendar Reddy, G., Srinu, G., Manjulatha, K., Venkata Prasad, J., Pramod Kumar, S., Srinivas, O., Iqbal, J. & Anil Kumar, K. (2010). Synlett, pp. 947–951. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
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We have synthesized and reported our serendipitous observations on the Diels-Alder reaction of 3-carbethoxy coumarin with furan, followed by a ring opening to yield Michael product, 3-carbethoxy-4-(2-furyl)-chroman-2-one in good yields.