Acta Cryst. (2010). E66, o567 [ doi:10.1107/S1600536810004423 ]
The title compound, C14H18O2, was obtained as a by-product during the preparation of carbofuran phenol. The two dihydrofuran rings are in envelope conformations.
After distillation of carbofuran phenol, the fraction at 433.15 K(3.33 K Pa) was cooled to room temperature, then the precipitate was emerged. The solid was purified by recrystallization from saturated ethyl acetate solution, giving the title compound as a colourless crystalline solid. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of an ethyl acetate solution at room temperature over a period of ten days. The identity of the title compound was confirmed by NMR and GC—MS spectroscopy.
All H atoms were placed in calculated positions, with C—H ranging from 0.95 Å to 0.99 Å and with Uiso(H) = 1.5Ueq(Cmethyl) or Uiso(H) = 1.2Ueq(C). The methyl groups were allowed to rotate but not to tip.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick 2008); program(s) used to refine structure: SHELXTL (Sheldrick 2008); molecular graphics: SHELXTL (Sheldrick 2008); software used to prepare material for publication: SHELXTL (Sheldrick 2008).
![[Figure 1]](./bt5185fig1thm.gif)
| Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids. |
![[Figure 2]](./bt5185fig2thm.gif)
| Fig. 2. A packing diagram for the title compound. H atoms bonded to C atoms have been omitted for clarity. |
| C14H18O2 | F(000) = 472 |
| Mr = 218.28 | Dx = 1.176 Mg m−3 |
| Monoclinic, P21/n | Melting point: 344.25 K |
| Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
| a = 8.7553 (6) Å | Cell parameters from 2852 reflections |
| b = 6.0721 (4) Å | θ = 2.5–27.0° |
| c = 23.2082 (17) Å | µ = 0.08 mm−1 |
| β = 92.186 (1)° | T = 173 K |
| V = 1232.92 (15) Å3 | Block, colourless |
| Z = 4 | 0.45 × 0.44 × 0.39 mm |
| Bruker SMART 1000 CCD diffractometer | 2662 independent reflections |
| Radiation source: fine-focus sealed tube | 1986 reflections with I > 2σ(I) |
| graphite | Rint = 0.022 |
| ω scans | θmax = 27.0°, θmin = 1.8° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −11→4 |
| Tmin = 0.966, Tmax = 0.971 | k = −7→7 |
| 5882 measured reflections | l = −27→29 |
| 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) = 0.131 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0698P)2 + 0.2701P] where P = (Fo2 + 2Fc2)/3 |
| 2662 reflections | (Δ/σ)max < 0.001 |
| 149 parameters | Δρmax = 0.25 e Å−3 |
| 0 restraints | Δρmin = −0.17 e Å−3 |
| C14H18O2 | V = 1232.92 (15) Å3 |
| Mr = 218.28 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 8.7553 (6) Å | µ = 0.08 mm−1 |
| b = 6.0721 (4) Å | T = 173 K |
| c = 23.2082 (17) Å | 0.45 × 0.44 × 0.39 mm |
| β = 92.186 (1)° |
| Bruker SMART 1000 CCD diffractometer | 2662 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1986 reflections with I > 2σ(I) |
| Tmin = 0.966, Tmax = 0.971 | Rint = 0.022 |
| 5882 measured reflections | θmax = 27.0° |
| R[F2 > 2σ(F2)] = 0.045 | H-atom parameters constrained |
| wR(F2) = 0.131 | Δρmax = 0.25 e Å−3 |
| S = 1.04 | Δρmin = −0.17 e Å−3 |
| 2662 reflections | Absolute structure: ? |
| 149 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Experimental. 1H NMR(300MHz, CDCl3), delta: 1.49(s, 12H, CH3); 2.99(s, 4H, CH2); 6.63(s, 2H, C6H2). GC-MS(m/z): 218, 203, 185, 175, 161. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 | −0.00729 (15) | 0.4208 (2) | 0.12566 (5) | 0.0263 (3) | |
| C2 | 0.10104 (15) | 0.2615 (2) | 0.13845 (6) | 0.0278 (3) | |
| C3 | 0.09122 (16) | 0.1360 (2) | 0.18790 (6) | 0.0303 (3) | |
| C4 | −0.02597 (17) | 0.1695 (3) | 0.22541 (6) | 0.0362 (4) | |
| H4 | −0.0320 | 0.0825 | 0.2593 | 0.043* | |
| C5 | −0.13474 (16) | 0.3316 (3) | 0.21305 (6) | 0.0370 (4) | |
| H5 | −0.2154 | 0.3568 | 0.2385 | 0.044* | |
| C6 | −0.12429 (15) | 0.4558 (2) | 0.16334 (6) | 0.0284 (3) | |
| C7 | −0.22006 (17) | 0.6411 (3) | 0.13820 (6) | 0.0344 (4) | |
| H7A | −0.1985 | 0.7813 | 0.1587 | 0.041* | |
| H7B | −0.3305 | 0.6076 | 0.1397 | 0.041* | |
| C8 | −0.16891 (15) | 0.6516 (2) | 0.07551 (6) | 0.0288 (3) | |
| C9 | −0.26730 (18) | 0.5101 (3) | 0.03545 (7) | 0.0365 (4) | |
| H9A | −0.2232 | 0.5065 | −0.0027 | 0.055* | |
| H9B | −0.3707 | 0.5718 | 0.0322 | 0.055* | |
| H9C | −0.2719 | 0.3601 | 0.0509 | 0.055* | |
| C10 | −0.1533 (2) | 0.8823 (3) | 0.05219 (8) | 0.0426 (4) | |
| H10A | −0.0817 | 0.9660 | 0.0772 | 0.064* | |
| H10B | −0.2534 | 0.9549 | 0.0511 | 0.064* | |
| H10C | −0.1148 | 0.8758 | 0.0131 | 0.064* | |
| C11 | 0.21711 (19) | −0.0321 (3) | 0.18774 (7) | 0.0436 (4) | |
| H11A | 0.1756 | −0.1821 | 0.1814 | 0.052* | |
| H11B | 0.2783 | −0.0295 | 0.2245 | 0.052* | |
| C12 | 0.31387 (17) | 0.0417 (3) | 0.13672 (7) | 0.0361 (4) | |
| C13 | 0.3435 (2) | −0.1428 (3) | 0.09508 (9) | 0.0541 (5) | |
| H13A | 0.2458 | −0.2021 | 0.0800 | 0.081* | |
| H13B | 0.4015 | −0.2597 | 0.1151 | 0.081* | |
| H13C | 0.4022 | −0.0865 | 0.0631 | 0.081* | |
| C14 | 0.4577 (2) | 0.1601 (3) | 0.15651 (8) | 0.0552 (5) | |
| H14A | 0.5094 | 0.2176 | 0.1229 | 0.083* | |
| H14B | 0.5258 | 0.0573 | 0.1775 | 0.083* | |
| H14C | 0.4317 | 0.2822 | 0.1819 | 0.083* | |
| O1 | −0.01419 (11) | 0.55235 (18) | 0.07800 (4) | 0.0333 (3) | |
| O2 | 0.21901 (12) | 0.2053 (2) | 0.10432 (4) | 0.0408 (3) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0245 (7) | 0.0291 (7) | 0.0254 (7) | −0.0008 (5) | 0.0020 (5) | −0.0003 (5) |
| C2 | 0.0230 (7) | 0.0322 (8) | 0.0282 (7) | 0.0018 (6) | 0.0028 (5) | −0.0035 (6) |
| C3 | 0.0259 (7) | 0.0317 (8) | 0.0329 (7) | −0.0001 (6) | −0.0033 (5) | 0.0010 (6) |
| C4 | 0.0309 (8) | 0.0484 (9) | 0.0295 (7) | −0.0024 (7) | 0.0010 (6) | 0.0120 (7) |
| C5 | 0.0260 (7) | 0.0565 (10) | 0.0288 (7) | 0.0044 (7) | 0.0065 (5) | 0.0053 (7) |
| C6 | 0.0241 (7) | 0.0341 (8) | 0.0272 (7) | 0.0020 (6) | 0.0015 (5) | −0.0024 (6) |
| C7 | 0.0321 (8) | 0.0383 (8) | 0.0330 (8) | 0.0093 (6) | 0.0025 (6) | −0.0032 (6) |
| C8 | 0.0242 (7) | 0.0285 (7) | 0.0339 (7) | 0.0040 (6) | 0.0018 (5) | 0.0005 (6) |
| C9 | 0.0379 (8) | 0.0350 (8) | 0.0364 (8) | −0.0012 (7) | −0.0006 (6) | −0.0028 (6) |
| C10 | 0.0421 (9) | 0.0302 (8) | 0.0547 (10) | −0.0037 (7) | −0.0068 (7) | 0.0061 (7) |
| C11 | 0.0390 (9) | 0.0416 (9) | 0.0501 (10) | 0.0108 (7) | 0.0015 (7) | 0.0082 (8) |
| C12 | 0.0266 (7) | 0.0388 (9) | 0.0425 (9) | 0.0087 (6) | −0.0041 (6) | −0.0028 (7) |
| C13 | 0.0450 (10) | 0.0521 (11) | 0.0649 (12) | 0.0124 (8) | −0.0022 (8) | −0.0167 (9) |
| C14 | 0.0455 (10) | 0.0595 (12) | 0.0595 (11) | −0.0107 (9) | −0.0124 (9) | 0.0016 (9) |
| O1 | 0.0268 (5) | 0.0397 (6) | 0.0339 (5) | 0.0067 (4) | 0.0074 (4) | 0.0099 (4) |
| O2 | 0.0341 (6) | 0.0526 (7) | 0.0365 (6) | 0.0184 (5) | 0.0103 (4) | 0.0057 (5) |
| C1—O1 | 1.3639 (16) | C9—H9A | 0.9800 |
| C1—C2 | 1.3792 (19) | C9—H9B | 0.9800 |
| C1—C6 | 1.3882 (19) | C9—H9C | 0.9800 |
| C2—O2 | 1.3685 (16) | C10—H10A | 0.9800 |
| C2—C3 | 1.383 (2) | C10—H10B | 0.9800 |
| C3—C4 | 1.386 (2) | C10—H10C | 0.9800 |
| C3—C11 | 1.502 (2) | C11—C12 | 1.548 (2) |
| C4—C5 | 1.392 (2) | C11—H11A | 0.9900 |
| C4—H4 | 0.9500 | C11—H11B | 0.9900 |
| C5—C6 | 1.384 (2) | C12—O2 | 1.4812 (18) |
| C5—H5 | 0.9500 | C12—C14 | 1.507 (2) |
| C6—C7 | 1.508 (2) | C12—C13 | 1.509 (2) |
| C7—C8 | 1.540 (2) | C13—H13A | 0.9800 |
| C7—H7A | 0.9900 | C13—H13B | 0.9800 |
| C7—H7B | 0.9900 | C13—H13C | 0.9800 |
| C8—O1 | 1.4816 (16) | C14—H14A | 0.9800 |
| C8—C10 | 1.510 (2) | C14—H14B | 0.9800 |
| C8—C9 | 1.511 (2) | C14—H14C | 0.9800 |
| O1—C1—C2 | 126.45 (12) | H9A—C9—H9C | 109.5 |
| O1—C1—C6 | 114.22 (12) | H9B—C9—H9C | 109.5 |
| C2—C1—C6 | 119.32 (13) | C8—C10—H10A | 109.5 |
| O2—C2—C1 | 125.32 (13) | C8—C10—H10B | 109.5 |
| O2—C2—C3 | 114.54 (12) | H10A—C10—H10B | 109.5 |
| C1—C2—C3 | 120.07 (13) | C8—C10—H10C | 109.5 |
| C2—C3—C4 | 120.76 (13) | H10A—C10—H10C | 109.5 |
| C2—C3—C11 | 107.66 (13) | H10B—C10—H10C | 109.5 |
| C4—C3—C11 | 131.47 (14) | C3—C11—C12 | 103.19 (12) |
| C3—C4—C5 | 119.45 (13) | C3—C11—H11A | 111.1 |
| C3—C4—H4 | 120.3 | C12—C11—H11A | 111.1 |
| C5—C4—H4 | 120.3 | C3—C11—H11B | 111.1 |
| C6—C5—C4 | 119.37 (13) | C12—C11—H11B | 111.1 |
| C6—C5—H5 | 120.3 | H11A—C11—H11B | 109.1 |
| C4—C5—H5 | 120.3 | O2—C12—C14 | 106.33 (13) |
| C5—C6—C1 | 121.03 (13) | O2—C12—C13 | 106.23 (13) |
| C5—C6—C7 | 132.51 (13) | C14—C12—C13 | 112.80 (15) |
| C1—C6—C7 | 106.46 (12) | O2—C12—C11 | 105.66 (11) |
| C6—C7—C8 | 102.64 (11) | C14—C12—C11 | 112.36 (14) |
| C6—C7—H7A | 111.2 | C13—C12—C11 | 112.79 (15) |
| C8—C7—H7A | 111.2 | C12—C13—H13A | 109.5 |
| C6—C7—H7B | 111.2 | C12—C13—H13B | 109.5 |
| C8—C7—H7B | 111.2 | H13A—C13—H13B | 109.5 |
| H7A—C7—H7B | 109.2 | C12—C13—H13C | 109.5 |
| O1—C8—C10 | 107.24 (12) | H13A—C13—H13C | 109.5 |
| O1—C8—C9 | 106.96 (11) | H13B—C13—H13C | 109.5 |
| C10—C8—C9 | 111.36 (12) | C12—C14—H14A | 109.5 |
| O1—C8—C7 | 104.17 (10) | C12—C14—H14B | 109.5 |
| C10—C8—C7 | 114.23 (13) | H14A—C14—H14B | 109.5 |
| C9—C8—C7 | 112.23 (12) | C12—C14—H14C | 109.5 |
| C8—C9—H9A | 109.5 | H14A—C14—H14C | 109.5 |
| C8—C9—H9B | 109.5 | H14B—C14—H14C | 109.5 |
| H9A—C9—H9B | 109.5 | C1—O1—C8 | 106.37 (10) |
| C8—C9—H9C | 109.5 | C2—O2—C12 | 107.10 (11) |
| O1—C1—C2—O2 | −1.5 (2) | C6—C7—C8—O1 | −23.68 (14) |
| C6—C1—C2—O2 | 177.75 (13) | C6—C7—C8—C10 | −140.34 (13) |
| O1—C1—C2—C3 | −178.26 (13) | C6—C7—C8—C9 | 91.68 (14) |
| C6—C1—C2—C3 | 1.0 (2) | C2—C3—C11—C12 | 8.91 (17) |
| O2—C2—C3—C4 | −177.69 (13) | C4—C3—C11—C12 | −174.97 (15) |
| C1—C2—C3—C4 | −0.6 (2) | C3—C11—C12—O2 | −13.11 (16) |
| O2—C2—C3—C11 | −1.07 (18) | C3—C11—C12—C14 | 102.42 (16) |
| C1—C2—C3—C11 | 176.00 (13) | C3—C11—C12—C13 | −128.73 (14) |
| C2—C3—C4—C5 | −0.1 (2) | C2—C1—O1—C8 | 165.26 (13) |
| C11—C3—C4—C5 | −175.75 (16) | C6—C1—O1—C8 | −14.05 (15) |
| C3—C4—C5—C6 | 0.3 (2) | C10—C8—O1—C1 | 144.79 (12) |
| C4—C5—C6—C1 | 0.1 (2) | C9—C8—O1—C1 | −95.65 (13) |
| C4—C5—C6—C7 | −179.27 (15) | C7—C8—O1—C1 | 23.36 (14) |
| O1—C1—C6—C5 | 178.59 (13) | C1—C2—O2—C12 | 175.32 (13) |
| C2—C1—C6—C5 | −0.8 (2) | C3—C2—O2—C12 | −7.79 (16) |
| O1—C1—C6—C7 | −1.89 (16) | C14—C12—O2—C2 | −106.65 (15) |
| C2—C1—C6—C7 | 178.75 (12) | C13—C12—O2—C2 | 132.97 (14) |
| C5—C6—C7—C8 | −164.44 (16) | C11—C12—O2—C2 | 12.94 (16) |
| C1—C6—C7—C8 | 16.11 (15) |
This work was supported by the Central University Basic Scientific Research Fund of Hunan University.
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Carbofuran phenol (systematic name: 2,2-dimethy-2,3-dihydrobenzofuran-7-ol) is an important intermediate to prepare Carbofuran (Xu et al., 2005), Carbosulfan, Benfuracarb, Furathiocarb and other large tonnage carbamate pesticides. It also can be used as pharmaceutical intermediate, as a high value-added fine chemical product. The title compound, 2,2,7,7-tetramethyl-2,3,6,7-tetrahydrobenzofuro[7,6-b]furan, was obtained as a byproduct during the preparation of carbofuran phenol.