Acta Cryst. (2011). E67, o58 [ doi:10.1107/S1600536810050610 ]
The title compound, C17H22O2, was semi-synthesized from a mixture of ![[alpha]](/logos/entities/alpha_rmgif.gif)
-atlantone (Z) and -atlantone (E), which were isolated from the essential oil of the Atlas cedar (cedrus atlantica). The molecule consists of fused six- and seven-membered rings. The seven-membered ring is in a screw-boat conformation.
In a reactor equipped with a stirring stick, containing 2 g (9,30 mmol) of 2-methyl-6-(4-methylphenyl) hept-2-en-4-one; 1,2 g of Lewis acid (AlCl3) and 30 ml of dichloromethane, we added drop wise with vigorous stirring 1 ml of acetyl chloride. The reaction mixture is heated to 323K in a water bath for one hour. After cooling, the reaction mixture was poured into 20 ml of iced water supplemented with 4 ml of concentrated hydrochloric acid. The reaction mixture was extracted three times with 20 ml of dichloromethane. The organic phases are combined, dried and evaporated under vacuum. Chromatography on silica gel of the residue obtained with hexane-ethyl acetate (98/2) as eluent, allowed us to isolate the pure 4-acethyl-aryl-himachal-9-one. The title compound was recrystallized in hexane.
All H atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl), 0.97 Å (methylene), 0.93Å (aromatic), 0.98Å (methine) with Uiso(H) = 1.2Ueq(C) or Uiso(H) = 1.5Ueq(methyl).
Data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); 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, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./lh5174fig1thm.gif)
| Fig. 1. Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii. |
| C17H22O2 | F(000) = 560 |
| Mr = 258.35 | Dx = 1.223 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 2855 reflections |
| a = 7.7996 (6) Å | θ = 3.5–29.3° |
| b = 18.3702 (10) Å | µ = 0.08 mm−1 |
| c = 9.9357 (6) Å | T = 180 K |
| β = 99.616 (7)° | Needle, colourless |
| V = 1403.59 (16) Å3 | 0.6 × 0.25 × 0.10 mm |
| Z = 4 |
| Oxford Diffraction Xcalibur Eos Gemini ultra diffractometer | 2196 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.054 |
| graphite | θmax = 26.4°, θmin = 3.5° |
| Detector resolution: 16.1978 pixels mm-1 | h = −9→9 |
| φ and ω scans | k = −22→22 |
| 14554 measured reflections | l = −12→13 |
| 2855 independent reflections |
| 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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.145 | H-atom parameters constrained |
| S = 1.08 | w = 1/[σ2(Fo2) + (0.0729P)2 + 0.4506P] where P = (Fo2 + 2Fc2)/3 |
| 2855 reflections | (Δ/σ)max < 0.001 |
| 177 parameters | Δρmax = 0.61 e Å−3 |
| 0 restraints | Δρmin = −0.29 e Å−3 |
| C17H22O2 | V = 1403.59 (16) Å3 |
| Mr = 258.35 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 7.7996 (6) Å | µ = 0.08 mm−1 |
| b = 18.3702 (10) Å | T = 180 K |
| c = 9.9357 (6) Å | 0.6 × 0.25 × 0.10 mm |
| β = 99.616 (7)° |
| Oxford Diffraction Xcalibur Eos Gemini ultra diffractometer | 2196 reflections with I > 2σ(I) |
| 14554 measured reflections | Rint = 0.054 |
| 2855 independent reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.052 | H-atom parameters constrained |
| wR(F2) = 0.145 | Δρmax = 0.61 e Å−3 |
| S = 1.08 | Δρmin = −0.29 e Å−3 |
| 2855 reflections | Absolute structure: ? |
| 177 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | 0.3403 (2) | 0.13187 (7) | 0.19877 (15) | 0.0192 (3) | |
| C3 | 0.3247 (2) | 0.09640 (8) | −0.04316 (15) | 0.0205 (3) | |
| C4 | 0.2676 (2) | 0.02663 (8) | −0.01250 (15) | 0.0204 (3) | |
| C5 | 0.2523 (2) | 0.01136 (8) | 0.12259 (16) | 0.0230 (3) | |
| H5 | 0.2154 | −0.0350 | 0.1424 | 0.028* | |
| C6 | 0.2887 (2) | 0.06101 (8) | 0.23016 (15) | 0.0217 (3) | |
| C2 | 0.3584 (2) | 0.14604 (8) | 0.06319 (15) | 0.0207 (3) | |
| H2 | 0.3958 | 0.1922 | 0.0430 | 0.025* | |
| C13 | 0.2253 (2) | −0.03137 (9) | −0.11877 (16) | 0.0261 (4) | |
| C14 | 0.1717 (2) | −0.10595 (9) | −0.07708 (18) | 0.0298 (4) | |
| H14C | 0.1449 | −0.1363 | −0.1565 | 0.045* | |
| H14B | 0.0710 | −0.1017 | −0.0338 | 0.045* | |
| H14A | 0.2653 | −0.1273 | −0.0145 | 0.045* | |
| C10 | 0.3481 (2) | 0.18511 (9) | 0.44504 (16) | 0.0279 (4) | |
| H10A | 0.4307 | 0.1503 | 0.4920 | 0.034* | |
| H10B | 0.3653 | 0.2309 | 0.4940 | 0.034* | |
| C11 | 0.3860 (2) | 0.19632 (8) | 0.29825 (16) | 0.0244 (4) | |
| C7 | 0.2791 (2) | 0.03531 (9) | 0.37574 (16) | 0.0279 (4) | |
| H7 | 0.3916 | 0.0462 | 0.4322 | 0.033* | |
| C8 | 0.1391 (2) | 0.07785 (9) | 0.43676 (17) | 0.0294 (4) | |
| H13A | 0.0269 | 0.0690 | 0.3805 | 0.035* | |
| H13B | 0.1342 | 0.0586 | 0.5270 | 0.035* | |
| C12 | 0.3533 (3) | 0.12064 (9) | −0.18269 (17) | 0.0296 (4) | |
| H12C | 0.4006 | 0.1690 | −0.1770 | 0.044* | |
| H12B | 0.2445 | 0.1203 | −0.2443 | 0.044* | |
| H12A | 0.4332 | 0.0880 | −0.2156 | 0.044* | |
| C9 | 0.1675 (2) | 0.15840 (9) | 0.44834 (17) | 0.0304 (4) | |
| C15 | 0.2465 (3) | −0.04610 (9) | 0.38933 (18) | 0.0344 (4) | |
| H15B | 0.1345 | −0.0583 | 0.3384 | 0.052* | |
| H15A | 0.2495 | −0.0581 | 0.4838 | 0.052* | |
| H15C | 0.3349 | −0.0731 | 0.3544 | 0.052* | |
| C16 | 0.2815 (3) | 0.26390 (9) | 0.23925 (19) | 0.0398 (5) | |
| H16A | 0.3121 | 0.2761 | 0.1523 | 0.060* | |
| H16B | 0.3081 | 0.3042 | 0.3008 | 0.060* | |
| H16C | 0.1593 | 0.2534 | 0.2280 | 0.060* | |
| C17 | 0.5811 (3) | 0.21235 (11) | 0.3114 (2) | 0.0401 (5) | |
| H17A | 0.6462 | 0.1694 | 0.3420 | 0.060* | |
| H17B | 0.6121 | 0.2509 | 0.3762 | 0.060* | |
| H17C | 0.6072 | 0.2268 | 0.2242 | 0.060* | |
| O1 | 0.0495 (2) | 0.19936 (8) | 0.45978 (19) | 0.0569 (5) | |
| O2 | 0.2338 (2) | −0.01978 (7) | −0.23812 (13) | 0.0451 (4) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| C1 | 0.0204 (8) | 0.0162 (6) | 0.0213 (7) | 0.0013 (6) | 0.0047 (6) | −0.0012 (5) |
| C3 | 0.0206 (8) | 0.0216 (7) | 0.0201 (7) | 0.0008 (6) | 0.0053 (6) | 0.0008 (6) |
| C4 | 0.0216 (8) | 0.0197 (7) | 0.0206 (7) | 0.0009 (6) | 0.0056 (6) | −0.0023 (6) |
| C5 | 0.0305 (9) | 0.0162 (7) | 0.0246 (8) | −0.0016 (6) | 0.0110 (6) | −0.0008 (6) |
| C6 | 0.0284 (8) | 0.0181 (7) | 0.0207 (7) | −0.0003 (6) | 0.0100 (6) | −0.0007 (6) |
| C2 | 0.0233 (8) | 0.0158 (7) | 0.0240 (8) | −0.0002 (6) | 0.0065 (6) | 0.0019 (5) |
| C13 | 0.0299 (9) | 0.0236 (7) | 0.0255 (8) | 0.0000 (6) | 0.0065 (7) | −0.0034 (6) |
| C14 | 0.0380 (10) | 0.0216 (8) | 0.0309 (9) | −0.0030 (7) | 0.0088 (8) | −0.0075 (6) |
| C10 | 0.0407 (10) | 0.0212 (7) | 0.0209 (8) | 0.0002 (7) | 0.0023 (7) | −0.0041 (6) |
| C11 | 0.0336 (9) | 0.0166 (7) | 0.0231 (8) | −0.0007 (6) | 0.0056 (7) | −0.0023 (6) |
| C7 | 0.0406 (10) | 0.0226 (7) | 0.0227 (8) | −0.0006 (7) | 0.0118 (7) | −0.0004 (6) |
| C8 | 0.0383 (10) | 0.0308 (9) | 0.0215 (8) | −0.0040 (7) | 0.0118 (7) | −0.0031 (6) |
| C12 | 0.0415 (10) | 0.0265 (8) | 0.0225 (8) | −0.0031 (7) | 0.0104 (7) | 0.0019 (6) |
| C9 | 0.0420 (11) | 0.0297 (8) | 0.0218 (8) | 0.0067 (7) | 0.0115 (7) | −0.0022 (6) |
| C15 | 0.0477 (11) | 0.0278 (8) | 0.0305 (9) | 0.0021 (8) | 0.0150 (8) | 0.0045 (7) |
| C16 | 0.0705 (14) | 0.0206 (8) | 0.0293 (9) | 0.0125 (8) | 0.0109 (9) | −0.0009 (7) |
| C17 | 0.0399 (11) | 0.0412 (10) | 0.0392 (10) | −0.0167 (9) | 0.0065 (8) | −0.0103 (8) |
| O1 | 0.0600 (10) | 0.0397 (8) | 0.0797 (12) | 0.0175 (7) | 0.0368 (9) | −0.0021 (7) |
| O2 | 0.0778 (11) | 0.0364 (7) | 0.0217 (6) | −0.0148 (7) | 0.0099 (6) | −0.0065 (5) |
| C1—C2 | 1.402 (2) | C11—C17 | 1.534 (3) |
| C1—C6 | 1.412 (2) | C11—C16 | 1.546 (2) |
| C1—C11 | 1.545 (2) | C7—C15 | 1.527 (2) |
| C3—C2 | 1.387 (2) | C7—C8 | 1.547 (2) |
| C3—C4 | 1.407 (2) | C7—H7 | 0.9800 |
| C3—C12 | 1.508 (2) | C8—C9 | 1.498 (2) |
| C4—C5 | 1.396 (2) | C8—H13A | 0.9700 |
| C4—C13 | 1.498 (2) | C8—H13B | 0.9700 |
| C5—C6 | 1.398 (2) | C12—H12C | 0.9600 |
| C5—H5 | 0.9300 | C12—H12B | 0.9600 |
| C6—C7 | 1.535 (2) | C12—H12A | 0.9600 |
| C2—H2 | 0.9300 | C9—O1 | 1.209 (2) |
| C13—O2 | 1.217 (2) | C15—H15B | 0.9600 |
| C13—C14 | 1.510 (2) | C15—H15A | 0.9600 |
| C14—H14C | 0.9600 | C15—H15C | 0.9600 |
| C14—H14B | 0.9600 | C16—H16A | 0.9600 |
| C14—H14A | 0.9600 | C16—H16B | 0.9600 |
| C10—C9 | 1.497 (3) | C16—H16C | 0.9600 |
| C10—C11 | 1.549 (2) | C17—H17A | 0.9600 |
| C10—H10A | 0.9700 | C17—H17B | 0.9600 |
| C10—H10B | 0.9700 | C17—H17C | 0.9600 |
| C2—C1—C6 | 117.47 (13) | C15—C7—C6 | 114.81 (13) |
| C2—C1—C11 | 115.01 (12) | C15—C7—C8 | 108.73 (14) |
| C6—C1—C11 | 127.49 (13) | C6—C7—C8 | 111.27 (13) |
| C2—C3—C4 | 117.42 (13) | C15—C7—H7 | 107.2 |
| C2—C3—C12 | 117.90 (14) | C6—C7—H7 | 107.2 |
| C4—C3—C12 | 124.68 (14) | C8—C7—H7 | 107.2 |
| C5—C4—C3 | 118.18 (13) | C9—C8—C7 | 115.09 (14) |
| C5—C4—C13 | 119.40 (13) | C9—C8—H13A | 108.5 |
| C3—C4—C13 | 122.41 (13) | C7—C8—H13A | 108.5 |
| C4—C5—C6 | 124.41 (14) | C9—C8—H13B | 108.5 |
| C4—C5—H5 | 117.8 | C7—C8—H13B | 108.5 |
| C6—C5—H5 | 117.8 | H13A—C8—H13B | 107.5 |
| C5—C6—C1 | 117.48 (13) | C3—C12—H12C | 109.5 |
| C5—C6—C7 | 118.96 (13) | C3—C12—H12B | 109.5 |
| C1—C6—C7 | 123.50 (13) | H12C—C12—H12B | 109.5 |
| C3—C2—C1 | 124.97 (14) | C3—C12—H12A | 109.5 |
| C3—C2—H2 | 117.5 | H12C—C12—H12A | 109.5 |
| C1—C2—H2 | 117.5 | H12B—C12—H12A | 109.5 |
| O2—C13—C4 | 121.39 (15) | O1—C9—C10 | 122.13 (16) |
| O2—C13—C14 | 119.23 (14) | O1—C9—C8 | 121.14 (18) |
| C4—C13—C14 | 119.37 (14) | C10—C9—C8 | 116.73 (15) |
| C13—C14—H14C | 109.5 | C7—C15—H15B | 109.5 |
| C13—C14—H14B | 109.5 | C7—C15—H15A | 109.5 |
| H14C—C14—H14B | 109.5 | H15B—C15—H15A | 109.5 |
| C13—C14—H14A | 109.5 | C7—C15—H15C | 109.5 |
| H14C—C14—H14A | 109.5 | H15B—C15—H15C | 109.5 |
| H14B—C14—H14A | 109.5 | H15A—C15—H15C | 109.5 |
| C9—C10—C11 | 113.10 (14) | C11—C16—H16A | 109.5 |
| C9—C10—H10A | 109.0 | C11—C16—H16B | 109.5 |
| C11—C10—H10A | 109.0 | H16A—C16—H16B | 109.5 |
| C9—C10—H10B | 109.0 | C11—C16—H16C | 109.5 |
| C11—C10—H10B | 109.0 | H16A—C16—H16C | 109.5 |
| H10A—C10—H10B | 107.8 | H16B—C16—H16C | 109.5 |
| C17—C11—C1 | 108.73 (13) | C11—C17—H17A | 109.5 |
| C17—C11—C16 | 109.32 (15) | C11—C17—H17B | 109.5 |
| C1—C11—C16 | 108.79 (14) | H17A—C17—H17B | 109.5 |
| C17—C11—C10 | 106.74 (14) | C11—C17—H17C | 109.5 |
| C1—C11—C10 | 116.12 (12) | H17A—C17—H17C | 109.5 |
| C16—C11—C10 | 106.99 (13) | H17B—C17—H17C | 109.5 |
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements.
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358.
Daunis, J., Jaquier, R., Lopez, H. & Viallefont, Ph. (1981). J. Chem. Res. pp. 0639-0649
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.
Loughzail, M., Mazoir, N., Maya, C. M., Berraho, M., Benharref, A. & Bouhmaida, N. (2009). Acta Cryst. E65, o4.
Mazoir, N., El Ammari, L., Bouhmaida, N., Dahaoui, S., Benharref, A. & Berraho, M. (2009). Acta Cryst. E65, o1269–o1270.
Oxford Diffraction (2010). CrystAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.
Plattier, M. & Teisseire, P. (1974). Recherches, 19, 131–144.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Son Bredenberg, J. B. & Erdtman, H. (1961). Acta Chem. Scand. 15, 685–688
α-Atlantone (Z) and α-atlantone (E) are the two isomeric sesquiterpene ketones which are constituents of the essential oil of Cedrus atlantica (3%) (Plattier & Teisseire 1974). The reactivity of these ketones has been studied by our team (Loughzail et al., 2009; Mazoir et al., 2009) in order to prepare products with high added value used in the cosmetics industry or in pharmacology. In the same context, we have synthesized the title compound (4-acethyl-arylhimachal-9-one) from a mixture of two isomers α- atlatones. The action of one equivalent of chloride cethyl in the presence of the Lewis acid AlCl3 on 2-methyl-6-(4-methylphenyl)hept-2-en-4-one, which was obtained from the mixture of two α- atlantones isomers (Mazoir et al., 2009) led to a yield of 35% at 4-acethyl-aryl-himachal-9-one, a derivative of the aryl-himachalene (Son Bredenberg & Erdtman, 1961; Daunis et al., 1981). The structure of this new derivative of aryl-himachalene was determined by 1H, 13C NMR spectral analysis and mass spectroscopy and confirmed by its single-crystal X-ray structure. The molecular structure of the title compound is shown in Fig.1. The benzene ring is essentially planar, whereas the seven-membered ring displays a screw boat conformation as indicated by Cremer & Pople (1975) puckering parameters QT = 0.9688 (2) Å and θ = 71.57 (10)°, φ2 = 168.10 (11)° and φ3 = -6.36 (4)°.