Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807037403/cs2043sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807037403/cs2043Isup2.hkl |
CCDC reference: 660192
1 g (4.16 mmol) of compound (A) was dissolved in 15 ml of methanol. The mixture was heated until total dissolution, and then left resting at 0°C for 1 h. All this allowed us, after filtering under reduced pressure, to prepare (1S,3R,6S)-3-chloro-trans-himachalene, (I) in 84% yield. Suitable crystals were obtained by evaporation of a hexane solution at 277 K. m.p. = 325–326 K (hexane); Spectroscopic analysis: 1H NMR (300 MHz, CDCl3) δ (p.p.m.):1.63 (3H12, s), 4.65, 4.67 (Ha-13, Hb-13, 2 s), 0.80, 0.90 (3H14, 3H15, 2 s); 13C NMR (75 MHz, CDCl3) δ (p.p.m.): 47.9 (C-1), 43.0 (C-2), 72.0 (C-3), 42.9 (C-4), 24.4 (C-5), 43.3 (C-6), 155.9 (C-7), 41.5 (C-8), 32.9 (C-9), 31.7 (C-10) 43.4 (C-11), 34.7 (C-12), 110.5 (C-13), 30.2 (C-14), 22.3 (C-15).
All H atoms were fixed geometrically and treated as riding with C—H = 0.99 Å (CH2), 1.0 Å(CH) or 0.98 Å (CH3) with Uiso(H) = 1.2Ueq(CH, CH2) or Uiso(H) = 1.5Ueq(CH3).
The isolated sesquiterpenes of Cedrus atlantica essential oils were the subject of hemisynthesis in order to prepare chlorinated sesquiterpenoid compounds (El Jamili et al., 2002; Dakir et al., 2004) in good yield. Indeed, these compounds were tested, using the food poisoning technique, for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al., 2005). Other molecules containing chlorine atom induces stalk-cell differentiation during development of Dictystelium discoideum (Kav et al., 1992).
We were interested in the study on the reactivity of compound (A) (Ourhriss et al., 2007) which has two chlorine atoms at different positions, 3 and 7 (Fig. 1). The dehydrohalogenation of (A) gave, after heating at reflux in methanol, the title compound (I) with high chemoselectivity. 1H and 13C NMR spectroscopy did not make it possible to identify the exact structure of this product. Single-crystal X-ray diffraction analysis allowed us to elucidate its configuration and to identify (I) as (1S,3R,6S)-3-chloro-trans-himachalene.
The molecule is built up from two fused six-membered and seven-membered rings (Fig. 2). The six membered ring has a perfect chair conformation as indicated by the total puckering amplitude QT= 0.560 (3) Å[0.546 (3) Å] and spherical polar angle θ=168.4 (3)° [174.1 (3)°] with φ= 117 (2)°[121 (3)°] whereas the seven-membered ring in the non disordered molecule displays a twist-chair conformation with QT= 0.807 (7) Å, θ= 36.7 (7)°, φ2= -179.8 (5)° and φ3= 120.8 (3)° (Cremer & Pople, 1975).
Owing to the presence of the Cl atom, the absolute configuration could be fully confirmed to be C1(S), C3(R) and C6(S) (Flack, 1983).
For general background see: El Jamili et al. (2002); Dakir et al. (2004); Daoubi et al. (2005); Kav et al. (1992). For a related structure see: Ourhriss et al. (2007). For related literature, see: Cremer & Pople (1975).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C15H25Cl | F(000) = 1056 |
Mr = 240.80 | Dx = 1.134 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 3489 reflections |
a = 6.0470 (2) Å | θ = 2.7–32.1° |
b = 15.7158 (7) Å | µ = 0.25 mm−1 |
c = 29.6845 (12) Å | T = 180 K |
V = 2821.02 (19) Å3 | Prism, colourless |
Z = 8 | 0.65 × 0.24 × 0.21 mm |
Oxford Diffraction CCD Xcalibur diffractometer | 6222 independent reflections |
Radiation source: fine-focus sealed tube | 3666 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
Detector resolution: 8.2632 pixels mm-1 | θmax = 27.1°, θmin = 2.7° |
ω and φ scans | h = −7→5 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | k = −20→20 |
Tmin = 0.756, Tmax = 1.000 | l = −38→38 |
23369 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0662P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
6222 reflections | Δρmax = 0.41 e Å−3 |
294 parameters | Δρmin = −0.39 e Å−3 |
15 restraints | Absolute structure: Flack (1983), based on 2652 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.11 (7) |
C15H25Cl | V = 2821.02 (19) Å3 |
Mr = 240.80 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.0470 (2) Å | µ = 0.25 mm−1 |
b = 15.7158 (7) Å | T = 180 K |
c = 29.6845 (12) Å | 0.65 × 0.24 × 0.21 mm |
Oxford Diffraction CCD Xcalibur diffractometer | 6222 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 3666 reflections with I > 2σ(I) |
Tmin = 0.756, Tmax = 1.000 | Rint = 0.047 |
23369 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.132 | Δρmax = 0.41 e Å−3 |
S = 1.01 | Δρmin = −0.39 e Å−3 |
6222 reflections | Absolute structure: Flack (1983), based on 2652 Friedel pairs |
294 parameters | Absolute structure parameter: −0.11 (7) |
15 restraints |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl2 | 0.17012 (12) | −0.00184 (5) | 0.82920 (3) | 0.0474 (2) | |
C1 | 0.5574 (5) | 0.12081 (18) | 0.87157 (9) | 0.0324 (7) | |
H1 | 0.4003 | 0.1220 | 0.8820 | 0.039* | |
C2 | 0.5564 (5) | 0.08395 (17) | 0.82356 (9) | 0.0340 (7) | |
H21 | 0.4669 | 0.1220 | 0.8042 | 0.041* | |
H22 | 0.7098 | 0.0852 | 0.8119 | 0.041* | |
C3 | 0.4693 (4) | −0.00486 (19) | 0.81847 (10) | 0.0341 (7) | |
C4 | 0.5669 (5) | −0.06490 (19) | 0.85311 (10) | 0.0394 (8) | |
H41 | 0.7214 | −0.0782 | 0.8446 | 0.047* | |
H42 | 0.4822 | −0.1188 | 0.8528 | 0.047* | |
C5 | 0.5647 (5) | −0.02863 (17) | 0.90055 (10) | 0.0383 (8) | |
H51 | 0.6399 | −0.0686 | 0.9213 | 0.046* | |
H52 | 0.4099 | −0.0220 | 0.9108 | 0.046* | |
C6 | 0.6811 (5) | 0.05764 (18) | 0.90211 (9) | 0.0335 (7) | |
H6 | 0.8301 | 0.0490 | 0.8882 | 0.040* | |
C7 | 0.7212 (6) | 0.0838 (2) | 0.95016 (11) | 0.0456 (9) | |
C8 | 0.5674 (8) | 0.1440 (2) | 0.97280 (11) | 0.0621 (11) | |
H81 | 0.5793 | 0.1370 | 1.0059 | 0.075* | |
H82 | 0.4135 | 0.1306 | 0.9639 | 0.075* | |
C9 | 0.6195 (10) | 0.2348 (2) | 0.96037 (12) | 0.0794 (14) | |
H91 | 0.5466 | 0.2727 | 0.9825 | 0.095* | |
H92 | 0.7810 | 0.2434 | 0.9633 | 0.095* | |
C10 | 0.5521 (7) | 0.2611 (2) | 0.91505 (12) | 0.0606 (11) | |
H10A | 0.5904 | 0.3221 | 0.9119 | 0.073* | |
H10B | 0.3889 | 0.2571 | 0.9137 | 0.073* | |
C11 | 0.6439 (5) | 0.21461 (19) | 0.87306 (10) | 0.0369 (7) | |
C12 | 0.4969 (6) | −0.0370 (2) | 0.77094 (10) | 0.0480 (9) | |
H12A | 0.4188 | 0.0010 | 0.7501 | 0.072* | |
H12B | 0.4353 | −0.0945 | 0.7686 | 0.072* | |
H12C | 0.6544 | −0.0383 | 0.7632 | 0.072* | |
C13 | 0.8968 (8) | 0.0533 (2) | 0.97185 (13) | 0.0701 (12) | |
H13A | 0.9248 | 0.0700 | 1.0021 | 0.084* | |
H13B | 0.9941 | 0.0148 | 0.9571 | 0.084* | |
C14 | 0.5492 (6) | 0.2663 (2) | 0.83362 (12) | 0.0525 (9) | |
H14A | 0.5889 | 0.3264 | 0.8373 | 0.079* | |
H14B | 0.3878 | 0.2607 | 0.8332 | 0.079* | |
H14C | 0.6104 | 0.2450 | 0.8052 | 0.079* | |
C15 | 0.8931 (5) | 0.2188 (2) | 0.87064 (13) | 0.0588 (10) | |
H15A | 0.9445 | 0.1878 | 0.8440 | 0.088* | |
H15B | 0.9565 | 0.1928 | 0.8977 | 0.088* | |
H15C | 0.9400 | 0.2783 | 0.8686 | 0.088* | |
Cl1A | 0.61711 (12) | 0.71053 (6) | 0.79807 (3) | 0.0478 (2) | |
C2A | 1.0131 (5) | 0.73751 (18) | 0.83943 (9) | 0.0317 (7) | |
H2A1 | 0.9427 | 0.7910 | 0.8496 | 0.038* | |
H2A2 | 1.1734 | 0.7487 | 0.8361 | 0.038* | |
C3A | 0.9197 (4) | 0.7146 (2) | 0.79321 (9) | 0.0367 (7) | |
C4A | 0.9978 (5) | 0.6273 (2) | 0.77819 (10) | 0.0448 (9) | |
H4A1 | 0.9157 | 0.6106 | 0.7507 | 0.054* | |
H4A2 | 1.1567 | 0.6305 | 0.7703 | 0.054* | |
C5A | 0.9659 (6) | 0.5603 (2) | 0.81364 (10) | 0.0464 (9) | |
H5A1 | 1.0302 | 0.5061 | 0.8029 | 0.056* | |
H5A2 | 0.8056 | 0.5513 | 0.8185 | 0.056* | |
C6A | 1.0739 (5) | 0.58486 (18) | 0.85846 (10) | 0.0371 (8) | |
H6A | 1.2356 | 0.5927 | 0.8528 | 0.044* | |
C7A | 1.0477 (6) | 0.5107 (2) | 0.89092 (12) | 0.0518 (9) | |
C8A | 0.8830 (13) | 0.5086 (7) | 0.9265 (2) | 0.0495 (10) | 0.52 |
H8A1 | 0.8651 | 0.4490 | 0.9367 | 0.059* | 0.52 |
H8A2 | 0.7396 | 0.5274 | 0.9138 | 0.059* | 0.52 |
C9A | 0.9364 (13) | 0.5634 (4) | 0.9670 (2) | 0.0495 (10) | 0.52 |
H9A1 | 0.8307 | 0.5491 | 0.9913 | 0.059* | 0.52 |
H9A2 | 1.0861 | 0.5481 | 0.9778 | 0.059* | 0.52 |
C10A | 0.9295 (12) | 0.6582 (4) | 0.9596 (2) | 0.0495 (10) | 0.52 |
H10C | 0.9698 | 0.6856 | 0.9885 | 0.059* | 0.52 |
H10D | 0.7737 | 0.6736 | 0.9534 | 0.059* | 0.52 |
C11A | 1.0726 (5) | 0.70010 (18) | 0.92240 (9) | 0.0325 (7) | |
C14A | 1.3124 (11) | 0.6824 (4) | 0.9264 (3) | 0.0462 (13) | 0.52 |
H14D | 1.3924 | 0.7134 | 0.9028 | 0.069* | 0.52 |
H14E | 1.3385 | 0.6212 | 0.9229 | 0.069* | 0.52 |
H14F | 1.3649 | 0.7010 | 0.9560 | 0.069* | 0.52 |
C15A | 1.0291 (11) | 0.7947 (5) | 0.9304 (3) | 0.0462 (13) | 0.52 |
H15D | 1.0688 | 0.8094 | 0.9614 | 0.069* | 0.52 |
H15E | 0.8720 | 0.8069 | 0.9254 | 0.069* | 0.52 |
H15F | 1.1185 | 0.8285 | 0.9095 | 0.069* | 0.52 |
C1A | 0.9818 (5) | 0.67051 (17) | 0.87616 (9) | 0.0287 (7) | |
H1A | 0.8187 | 0.6627 | 0.8799 | 0.034* | |
C8B | 0.8358 (14) | 0.5152 (7) | 0.9182 (3) | 0.0495 (10) | 0.48 |
H8B1 | 0.7978 | 0.4578 | 0.9296 | 0.059* | 0.48 |
H8B2 | 0.7132 | 0.5349 | 0.8987 | 0.059* | 0.48 |
C9B | 0.8644 (13) | 0.5785 (5) | 0.9593 (3) | 0.0495 (10) | 0.48 |
H9B1 | 0.7345 | 0.6168 | 0.9598 | 0.059* | 0.48 |
H9B2 | 0.8606 | 0.5445 | 0.9874 | 0.059* | 0.48 |
C10B | 1.0686 (13) | 0.6326 (4) | 0.9603 (2) | 0.0495 (10) | 0.48 |
H10E | 1.2002 | 0.5956 | 0.9574 | 0.059* | 0.48 |
H10F | 1.0776 | 0.6618 | 0.9898 | 0.059* | 0.48 |
C14B | 1.3206 (12) | 0.7264 (5) | 0.9206 (3) | 0.0462 (13) | 0.48 |
H14G | 1.3760 | 0.7349 | 0.9513 | 0.069* | 0.48 |
H14H | 1.3356 | 0.7795 | 0.9035 | 0.069* | 0.48 |
H14I | 1.4063 | 0.6815 | 0.9058 | 0.069* | 0.48 |
C15B | 0.9445 (12) | 0.7763 (5) | 0.9386 (3) | 0.0462 (13) | 0.48 |
H15G | 1.0012 | 0.7942 | 0.9681 | 0.069* | 0.48 |
H15H | 0.7877 | 0.7614 | 0.9414 | 0.069* | 0.48 |
H15I | 0.9611 | 0.8230 | 0.9170 | 0.069* | 0.48 |
C12A | 0.9693 (6) | 0.7850 (2) | 0.75919 (11) | 0.0520 (9) | |
H12D | 1.1293 | 0.7885 | 0.7543 | 0.078* | |
H12E | 0.9152 | 0.8395 | 0.7709 | 0.078* | |
H12F | 0.8953 | 0.7722 | 0.7306 | 0.078* | |
C13A | 1.1925 (9) | 0.4474 (2) | 0.88913 (15) | 0.0889 (16) | |
H13C | 1.1861 | 0.4028 | 0.9107 | 0.107* | |
H13D | 1.3026 | 0.4467 | 0.8663 | 0.107* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl2 | 0.0276 (4) | 0.0498 (5) | 0.0649 (5) | −0.0004 (4) | 0.0030 (4) | −0.0004 (4) |
C1 | 0.0256 (16) | 0.0303 (16) | 0.0412 (17) | 0.0049 (14) | 0.0028 (14) | 0.0051 (14) |
C2 | 0.0289 (16) | 0.0327 (16) | 0.0403 (17) | 0.0018 (14) | 0.0020 (14) | 0.0068 (14) |
C3 | 0.0228 (14) | 0.0345 (16) | 0.0449 (17) | 0.0037 (15) | 0.0040 (13) | 0.0004 (15) |
C4 | 0.0344 (18) | 0.0306 (16) | 0.0532 (19) | 0.0034 (15) | 0.0054 (16) | −0.0015 (15) |
C5 | 0.0431 (19) | 0.0285 (16) | 0.0432 (18) | 0.0067 (15) | 0.0044 (16) | 0.0083 (14) |
C6 | 0.0263 (15) | 0.0369 (17) | 0.0372 (16) | 0.0071 (15) | 0.0050 (14) | 0.0029 (14) |
C7 | 0.051 (2) | 0.0402 (19) | 0.046 (2) | 0.0000 (17) | −0.0070 (18) | 0.0090 (16) |
C8 | 0.094 (3) | 0.051 (2) | 0.041 (2) | 0.010 (2) | 0.013 (2) | −0.0008 (17) |
C9 | 0.127 (4) | 0.053 (2) | 0.059 (3) | 0.018 (3) | 0.013 (3) | −0.005 (2) |
C10 | 0.077 (3) | 0.0359 (19) | 0.068 (2) | −0.003 (2) | −0.007 (2) | −0.0039 (18) |
C11 | 0.0292 (16) | 0.0320 (16) | 0.0495 (18) | 0.0028 (15) | 0.0000 (15) | 0.0026 (15) |
C12 | 0.051 (2) | 0.047 (2) | 0.0461 (19) | 0.0050 (18) | 0.0036 (18) | −0.0039 (16) |
C13 | 0.089 (3) | 0.060 (2) | 0.061 (2) | 0.010 (3) | −0.026 (2) | 0.002 (2) |
C14 | 0.056 (2) | 0.0362 (18) | 0.065 (2) | −0.0034 (17) | −0.003 (2) | 0.0113 (17) |
C15 | 0.0369 (19) | 0.044 (2) | 0.096 (3) | −0.0079 (18) | −0.005 (2) | 0.011 (2) |
Cl1A | 0.0273 (4) | 0.0734 (6) | 0.0428 (4) | 0.0024 (4) | −0.0038 (4) | −0.0059 (4) |
C2A | 0.0239 (15) | 0.0372 (16) | 0.0340 (16) | −0.0006 (13) | 0.0011 (13) | −0.0088 (13) |
C3A | 0.0222 (14) | 0.054 (2) | 0.0334 (16) | −0.0012 (16) | 0.0013 (13) | −0.0075 (16) |
C4A | 0.0354 (18) | 0.062 (2) | 0.0371 (17) | 0.0020 (18) | 0.0024 (16) | −0.0217 (17) |
C5A | 0.044 (2) | 0.0458 (19) | 0.049 (2) | −0.0010 (17) | −0.0041 (16) | −0.0180 (17) |
C6A | 0.0301 (17) | 0.0368 (18) | 0.0442 (18) | 0.0043 (15) | 0.0017 (15) | −0.0124 (15) |
C7A | 0.062 (2) | 0.0309 (18) | 0.062 (2) | 0.0065 (19) | −0.026 (2) | −0.0100 (17) |
C8A | 0.051 (3) | 0.056 (2) | 0.0415 (17) | −0.005 (2) | −0.0182 (18) | 0.0160 (15) |
C9A | 0.051 (3) | 0.056 (2) | 0.0415 (17) | −0.005 (2) | −0.0182 (18) | 0.0160 (15) |
C10A | 0.051 (3) | 0.056 (2) | 0.0415 (17) | −0.005 (2) | −0.0182 (18) | 0.0160 (15) |
C11A | 0.0317 (16) | 0.0375 (17) | 0.0283 (15) | 0.0021 (15) | −0.0019 (13) | −0.0042 (13) |
C14A | 0.037 (2) | 0.050 (3) | 0.051 (2) | 0.011 (3) | −0.0151 (18) | −0.023 (2) |
C15A | 0.037 (2) | 0.050 (3) | 0.051 (2) | 0.011 (3) | −0.0151 (18) | −0.023 (2) |
C1A | 0.0210 (14) | 0.0341 (16) | 0.0310 (15) | 0.0010 (13) | 0.0014 (13) | −0.0045 (13) |
C8B | 0.051 (3) | 0.056 (2) | 0.0415 (17) | −0.005 (2) | −0.0182 (18) | 0.0160 (15) |
C9B | 0.051 (3) | 0.056 (2) | 0.0415 (17) | −0.005 (2) | −0.0182 (18) | 0.0160 (15) |
C10B | 0.051 (3) | 0.056 (2) | 0.0415 (17) | −0.005 (2) | −0.0182 (18) | 0.0160 (15) |
C14B | 0.037 (2) | 0.050 (3) | 0.051 (2) | 0.011 (3) | −0.0151 (18) | −0.023 (2) |
C15B | 0.037 (2) | 0.050 (3) | 0.051 (2) | 0.011 (3) | −0.0151 (18) | −0.023 (2) |
C12A | 0.044 (2) | 0.071 (2) | 0.0409 (19) | 0.000 (2) | 0.0039 (16) | 0.0043 (18) |
C13A | 0.129 (4) | 0.050 (2) | 0.087 (3) | 0.035 (3) | −0.033 (3) | −0.014 (2) |
Cl2—C3 | 1.838 (3) | C4A—H4A2 | 0.9900 |
C1—C2 | 1.538 (4) | C5A—C6A | 1.531 (4) |
C1—C6 | 1.538 (4) | C5A—H5A1 | 0.9900 |
C1—C11 | 1.565 (4) | C5A—H5A2 | 0.9900 |
C1—H1 | 1.0000 | C6A—C7A | 1.521 (4) |
C2—C3 | 1.499 (4) | C6A—C1A | 1.549 (4) |
C2—H21 | 0.9900 | C6A—H6A | 1.0000 |
C2—H22 | 0.9900 | C7A—C13A | 1.326 (5) |
C3—C12 | 1.508 (4) | C7A—C8A | 1.451 (9) |
C3—C4 | 1.515 (4) | C7A—C8B | 1.518 (10) |
C4—C5 | 1.519 (4) | C8A—C9A | 1.515 (8) |
C4—H41 | 0.9900 | C8A—H8A1 | 0.9900 |
C4—H42 | 0.9900 | C8A—H8A2 | 0.9900 |
C5—C6 | 1.528 (4) | C9A—C10A | 1.507 (9) |
C5—H51 | 0.9900 | C9A—H9A1 | 0.9900 |
C5—H52 | 0.9900 | C9A—H9A2 | 0.9900 |
C6—C7 | 1.504 (4) | C10A—C11A | 1.549 (7) |
C6—H6 | 1.0000 | C10A—H10C | 0.9900 |
C7—C13 | 1.331 (5) | C10A—H10D | 0.9900 |
C7—C8 | 1.488 (5) | C11A—C14A | 1.481 (7) |
C8—C9 | 1.507 (5) | C11A—C15B | 1.506 (8) |
C8—H81 | 0.9900 | C11A—C15A | 1.528 (7) |
C8—H82 | 0.9900 | C11A—C10B | 1.547 (6) |
C9—C10 | 1.465 (5) | C11A—C1A | 1.550 (4) |
C9—H91 | 0.9900 | C11A—C14B | 1.557 (8) |
C9—H92 | 0.9900 | C14A—H14D | 0.9800 |
C10—C11 | 1.548 (4) | C14A—H14E | 0.9800 |
C10—H10A | 0.9900 | C14A—H14F | 0.9800 |
C10—H10B | 0.9900 | C15A—H15D | 0.9800 |
C11—C15 | 1.510 (4) | C15A—H15E | 0.9800 |
C11—C14 | 1.536 (4) | C15A—H15F | 0.9800 |
C12—H12A | 0.9800 | C1A—H1A | 1.0000 |
C12—H12B | 0.9800 | C8B—C9B | 1.583 (9) |
C12—H12C | 0.9800 | C8B—H8B1 | 0.9900 |
C13—H13A | 0.9500 | C8B—H8B2 | 0.9900 |
C13—H13B | 0.9500 | C9B—C10B | 1.500 (10) |
C14—H14A | 0.9800 | C9B—H9B1 | 0.9900 |
C14—H14B | 0.9800 | C9B—H9B2 | 0.9900 |
C14—H14C | 0.9800 | C10B—H10E | 0.9900 |
C15—H15A | 0.9800 | C10B—H10F | 0.9900 |
C15—H15B | 0.9800 | C14B—H14G | 0.9800 |
C15—H15C | 0.9800 | C14B—H14H | 0.9800 |
Cl1A—C3A | 1.837 (3) | C14B—H14I | 0.9800 |
C2A—C3A | 1.527 (4) | C15B—H15G | 0.9800 |
C2A—C1A | 1.528 (4) | C15B—H15H | 0.9800 |
C2A—H2A1 | 0.9900 | C15B—H15I | 0.9800 |
C2A—H2A2 | 0.9900 | C12A—H12D | 0.9800 |
C3A—C4A | 1.518 (4) | C12A—H12E | 0.9800 |
C3A—C12A | 1.527 (4) | C12A—H12F | 0.9800 |
C4A—C5A | 1.501 (4) | C13A—H13C | 0.9500 |
C4A—H4A1 | 0.9900 | C13A—H13D | 0.9500 |
C2—C1—C6 | 107.8 (2) | C4A—C5A—H5A2 | 109.2 |
C2—C1—C11 | 112.5 (2) | C6A—C5A—H5A2 | 109.2 |
C6—C1—C11 | 115.4 (2) | H5A1—C5A—H5A2 | 107.9 |
C2—C1—H1 | 106.9 | C7A—C6A—C5A | 108.3 (2) |
C6—C1—H1 | 106.9 | C7A—C6A—C1A | 114.4 (2) |
C11—C1—H1 | 106.9 | C5A—C6A—C1A | 111.1 (2) |
C3—C2—C1 | 116.4 (2) | C7A—C6A—H6A | 107.6 |
C3—C2—H21 | 108.2 | C5A—C6A—H6A | 107.6 |
C1—C2—H21 | 108.2 | C1A—C6A—H6A | 107.6 |
C3—C2—H22 | 108.2 | C13A—C7A—C8A | 117.7 (5) |
C1—C2—H22 | 108.2 | C13A—C7A—C8B | 127.9 (6) |
H21—C2—H22 | 107.3 | C8A—C7A—C8B | 14.9 (5) |
C2—C3—C12 | 111.5 (3) | C13A—C7A—C6A | 118.8 (4) |
C2—C3—C4 | 112.0 (2) | C8A—C7A—C6A | 123.3 (5) |
C12—C3—C4 | 112.5 (3) | C8B—C7A—C6A | 113.0 (5) |
C2—C3—Cl2 | 107.7 (2) | C7A—C8A—C9A | 114.8 (6) |
C12—C3—Cl2 | 106.2 (2) | C7A—C8A—H8A1 | 108.6 |
C4—C3—Cl2 | 106.4 (2) | C9A—C8A—H8A1 | 108.6 |
C3—C4—C5 | 113.1 (2) | C7A—C8A—H8A2 | 108.6 |
C3—C4—H41 | 109.0 | C9A—C8A—H8A2 | 108.6 |
C5—C4—H41 | 109.0 | H8A1—C8A—H8A2 | 107.6 |
C3—C4—H42 | 109.0 | C10A—C9A—C8A | 116.1 (6) |
C5—C4—H42 | 109.0 | C10A—C9A—H9A1 | 108.3 |
H41—C4—H42 | 107.8 | C8A—C9A—H9A1 | 108.3 |
C4—C5—C6 | 110.9 (2) | C10A—C9A—H9A2 | 108.3 |
C4—C5—H51 | 109.5 | C8A—C9A—H9A2 | 108.3 |
C6—C5—H51 | 109.5 | H9A1—C9A—H9A2 | 107.4 |
C4—C5—H52 | 109.5 | C9A—C10A—C11A | 120.6 (6) |
C6—C5—H52 | 109.5 | C9A—C10A—H10C | 107.2 |
H51—C5—H52 | 108.0 | C11A—C10A—H10C | 107.2 |
C7—C6—C5 | 110.2 (2) | C9A—C10A—H10D | 107.2 |
C7—C6—C1 | 117.5 (2) | C11A—C10A—H10D | 107.2 |
C5—C6—C1 | 109.3 (2) | H10C—C10A—H10D | 106.8 |
C7—C6—H6 | 106.4 | C14A—C11A—C15B | 128.8 (5) |
C5—C6—H6 | 106.4 | C14A—C11A—C15A | 109.8 (4) |
C1—C6—H6 | 106.4 | C15B—C11A—C15A | 24.2 (4) |
C13—C7—C8 | 120.6 (3) | C14A—C11A—C10B | 80.1 (5) |
C13—C7—C6 | 119.3 (3) | C15B—C11A—C10B | 107.7 (5) |
C8—C7—C6 | 120.1 (3) | C15A—C11A—C10B | 123.4 (5) |
C7—C8—C9 | 111.2 (3) | C14A—C11A—C10A | 114.2 (5) |
C7—C8—H81 | 109.4 | C15B—C11A—C10A | 79.8 (4) |
C9—C8—H81 | 109.4 | C15A—C11A—C10A | 101.9 (4) |
C7—C8—H82 | 109.4 | C10B—C11A—C10A | 35.1 (3) |
C9—C8—H82 | 109.4 | C14A—C11A—C1A | 111.2 (3) |
H81—C8—H82 | 108.0 | C15B—C11A—C1A | 109.9 (4) |
C10—C9—C8 | 115.7 (4) | C15A—C11A—C1A | 111.6 (4) |
C10—C9—H91 | 108.4 | C10B—C11A—C1A | 115.7 (3) |
C8—C9—H91 | 108.4 | C10A—C11A—C1A | 107.8 (3) |
C10—C9—H92 | 108.4 | C14A—C11A—C14B | 27.0 (3) |
C8—C9—H92 | 108.4 | C15B—C11A—C14B | 107.2 (5) |
H91—C9—H92 | 107.4 | C15A—C11A—C14B | 85.0 (4) |
C9—C10—C11 | 120.4 (3) | C10B—C11A—C14B | 102.9 (4) |
C9—C10—H10A | 107.2 | C10A—C11A—C14B | 132.5 (5) |
C11—C10—H10A | 107.2 | C1A—C11A—C14B | 113.0 (4) |
C9—C10—H10B | 107.2 | C11A—C14A—H14D | 109.5 |
C11—C10—H10B | 107.2 | C11A—C14A—H14E | 109.5 |
H10A—C10—H10B | 106.9 | C11A—C14A—H14F | 109.5 |
C15—C11—C14 | 108.2 (3) | C11A—C15A—H15D | 109.5 |
C15—C11—C10 | 112.1 (3) | C11A—C15A—H15E | 109.5 |
C14—C11—C10 | 103.3 (3) | C11A—C15A—H15F | 109.5 |
C15—C11—C1 | 111.9 (3) | C2A—C1A—C6A | 108.2 (2) |
C14—C11—C1 | 110.6 (2) | C2A—C1A—C11A | 112.4 (2) |
C10—C11—C1 | 110.3 (2) | C6A—C1A—C11A | 115.7 (2) |
C3—C12—H12A | 109.5 | C2A—C1A—H1A | 106.7 |
C3—C12—H12B | 109.5 | C6A—C1A—H1A | 106.7 |
H12A—C12—H12B | 109.5 | C11A—C1A—H1A | 106.7 |
C3—C12—H12C | 109.5 | C7A—C8B—C9B | 110.4 (6) |
H12A—C12—H12C | 109.5 | C7A—C8B—H8B1 | 109.6 |
H12B—C12—H12C | 109.5 | C9B—C8B—H8B1 | 109.6 |
C7—C13—H13A | 120.0 | C7A—C8B—H8B2 | 109.6 |
C7—C13—H13B | 120.0 | C9B—C8B—H8B2 | 109.6 |
H13A—C13—H13B | 120.0 | H8B1—C8B—H8B2 | 108.1 |
C11—C14—H14A | 109.5 | C10B—C9B—C8B | 117.5 (7) |
C11—C14—H14B | 109.5 | C10B—C9B—H9B1 | 107.9 |
H14A—C14—H14B | 109.5 | C8B—C9B—H9B1 | 107.9 |
C11—C14—H14C | 109.5 | C10B—C9B—H9B2 | 107.9 |
H14A—C14—H14C | 109.5 | C8B—C9B—H9B2 | 107.9 |
H14B—C14—H14C | 109.5 | H9B1—C9B—H9B2 | 107.2 |
C11—C15—H15A | 109.5 | C9B—C10B—C11A | 112.8 (5) |
C11—C15—H15B | 109.5 | C9B—C10B—H10E | 109.0 |
H15A—C15—H15B | 109.5 | C11A—C10B—H10E | 109.0 |
C11—C15—H15C | 109.5 | C9B—C10B—H10F | 109.0 |
H15A—C15—H15C | 109.5 | C11A—C10B—H10F | 109.0 |
H15B—C15—H15C | 109.5 | H10E—C10B—H10F | 107.8 |
C3A—C2A—C1A | 115.7 (2) | C11A—C14B—H14G | 109.5 |
C3A—C2A—H2A1 | 108.4 | C11A—C14B—H14H | 109.5 |
C1A—C2A—H2A1 | 108.4 | H14G—C14B—H14H | 109.5 |
C3A—C2A—H2A2 | 108.4 | C11A—C14B—H14I | 109.5 |
C1A—C2A—H2A2 | 108.4 | H14G—C14B—H14I | 109.5 |
H2A1—C2A—H2A2 | 107.4 | H14H—C14B—H14I | 109.5 |
C4A—C3A—C2A | 111.2 (2) | C11A—C15B—H15G | 109.5 |
C4A—C3A—C12A | 113.5 (2) | C11A—C15B—H15H | 109.5 |
C2A—C3A—C12A | 110.6 (2) | H15G—C15B—H15H | 109.5 |
C4A—C3A—Cl1A | 107.5 (2) | C11A—C15B—H15I | 109.5 |
C2A—C3A—Cl1A | 107.83 (19) | H15G—C15B—H15I | 109.5 |
C12A—C3A—Cl1A | 105.9 (2) | H15H—C15B—H15I | 109.5 |
C5A—C4A—C3A | 112.8 (2) | C3A—C12A—H12D | 109.5 |
C5A—C4A—H4A1 | 109.0 | C3A—C12A—H12E | 109.5 |
C3A—C4A—H4A1 | 109.0 | H12D—C12A—H12E | 109.5 |
C5A—C4A—H4A2 | 109.0 | C3A—C12A—H12F | 109.5 |
C3A—C4A—H4A2 | 109.0 | H12D—C12A—H12F | 109.5 |
H4A1—C4A—H4A2 | 107.8 | H12E—C12A—H12F | 109.5 |
C4A—C5A—C6A | 112.2 (3) | C7A—C13A—H13C | 120.0 |
C4A—C5A—H5A1 | 109.2 | C7A—C13A—H13D | 120.0 |
C6A—C5A—H5A1 | 109.2 | H13C—C13A—H13D | 120.0 |
Experimental details
Crystal data | |
Chemical formula | C15H25Cl |
Mr | 240.80 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 180 |
a, b, c (Å) | 6.0470 (2), 15.7158 (7), 29.6845 (12) |
V (Å3) | 2821.02 (19) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.65 × 0.24 × 0.21 |
Data collection | |
Diffractometer | Oxford Diffraction CCD Xcalibur |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.756, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23369, 6222, 3666 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.132, 1.01 |
No. of reflections | 6222 |
No. of parameters | 294 |
No. of restraints | 15 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.39 |
Absolute structure | Flack (1983), based on 2652 Friedel pairs |
Absolute structure parameter | −0.11 (7) |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
The isolated sesquiterpenes of Cedrus atlantica essential oils were the subject of hemisynthesis in order to prepare chlorinated sesquiterpenoid compounds (El Jamili et al., 2002; Dakir et al., 2004) in good yield. Indeed, these compounds were tested, using the food poisoning technique, for their potential antifungal activity against the phytopathogen Botrytis cinerea (Daoubi et al., 2005). Other molecules containing chlorine atom induces stalk-cell differentiation during development of Dictystelium discoideum (Kav et al., 1992).
We were interested in the study on the reactivity of compound (A) (Ourhriss et al., 2007) which has two chlorine atoms at different positions, 3 and 7 (Fig. 1). The dehydrohalogenation of (A) gave, after heating at reflux in methanol, the title compound (I) with high chemoselectivity. 1H and 13C NMR spectroscopy did not make it possible to identify the exact structure of this product. Single-crystal X-ray diffraction analysis allowed us to elucidate its configuration and to identify (I) as (1S,3R,6S)-3-chloro-trans-himachalene.
The molecule is built up from two fused six-membered and seven-membered rings (Fig. 2). The six membered ring has a perfect chair conformation as indicated by the total puckering amplitude QT= 0.560 (3) Å[0.546 (3) Å] and spherical polar angle θ=168.4 (3)° [174.1 (3)°] with φ= 117 (2)°[121 (3)°] whereas the seven-membered ring in the non disordered molecule displays a twist-chair conformation with QT= 0.807 (7) Å, θ= 36.7 (7)°, φ2= -179.8 (5)° and φ3= 120.8 (3)° (Cremer & Pople, 1975).
Owing to the presence of the Cl atom, the absolute configuration could be fully confirmed to be C1(S), C3(R) and C6(S) (Flack, 1983).