organic compounds
(1S,2R,3S,6S,7R)-3,7,11,11-Tetramethyl-6,7-epoxybicyclo[5.4.0]undecane-2-ol
aLaboratoire de Chimie des Substances Naturelles, "Unité Associé au CNRST (URAC16)", Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, 40000 Marrakech, Morocco, and bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, BP 1014, Avenue Ibn Battouta, Rabat, Morocco
*Correspondence e-mail: loubidim@gmail.com
The title compound, C15H26O2, was synthesized from β-himachalene (3,5,5,9-tetramethyl-2,4a,5,6,7,8-hexahydro-1H-benzocycloheptene), which was isolated from the Atlas cedar (cedrus atlantica). The molecule is built up from a seven-membered ring to which a six- and a three-membered ring are fused. The seven- and six-membered rings each have a twist-boat conformation. In the crystal, O—H⋯O hydrogen bonds link the molecules into zigzag chains running along the b-axis direction.
CCDC reference: 997713
Related literature
For background to β-himachalene, see: El Haib et al.;(2011). For the reactivity of this sesquiterpene and its derivatives, see: El Jamili et al. (2002); Benharref et al. (2013); Ourhriss et al. (2013). For their potential antifungal activity against the phytopathogen Botrytis cinerea, see: Daoubi et al. (2004). For puckering parameters, see: Cremer & Pople (1975).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2009); cell SAINT (Bruker, 2009); data reduction: SAINT; 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, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 997713
10.1107/S1600536814008642/bt6976sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814008642/bt6976Isup2.hkl
Diborane is prepared by addition at 0 °C of 2.5 g (17 mmol) of boron trifluoride etherate in 0.5 g (12.6 mmol) of sodium borohydride in 30 ml of diglyme. Diborane formed is driven by a stream of dry nitrogen in 2 g (10 mmol) of β-himachalene dissolved in 20 ml of tetrahydrofuran at 273K. This takes about 4 h. 2 ml of sodium hydroxide 3 N is then added carefully between 263K and 273K in 15 minutes and then 2 ml of 30% hydrogen peroxide in the vicinity of 298K. The reaction mixture was then extracted with diethyl ether, the organic phase is washed to neutrality and the solvent was evaporated under vacuum. The residue obtained is chromatographed on a column of silica gel with hexane-ethyl acetate (95:5), which allowed the isolation of pure (1S, 2R, 3S, 6S, 7R)-6,7-epoxy-3,7,11,11- tetramethylbicyclo[5.4.0] undecane-2-ol with a yield of 25% (600 mg 2.5 mmol). The title compound was recrystallized from its cyclohexane solution.
Except H11, which was freely refined, all H atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl),0.97 Å (methylene), 0.98 Å (methine) with Uiso(H) = 1.2Ueq(methylene, methine) or Uiso(H) = 1.5Ueq(methyl). The methyl groups were allowed to rotate, but not to tip. In the absence of significant
the could not be reliably determined and any references to the were removed. The of the chiral centres was arbitrarily set.Data collection: APEX2 (Bruker, 2009); cell
SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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, 2012); software used to prepare material for publication: PLATON (Spek, 2009) and publCIF (Westrip, 2010).C15H26O2 | F(000) = 264 |
Mr = 238.36 | Dx = 1.153 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 3036 reflections |
a = 5.9617 (10) Å | θ = 2.7–27.1° |
b = 12.068 (2) Å | µ = 0.07 mm−1 |
c = 9.5909 (15) Å | T = 298 K |
β = 95.789 (8)° | Needle, colourless |
V = 686.48 (19) Å3 | 0.38 × 0.11 × 0.10 mm |
Z = 2 |
Bruker X8 APEX diffractometer | 2698 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 27.1°, θmin = 2.7° |
ϕ and ω scans | h = −7→7 |
11541 measured reflections | k = −15→15 |
3036 independent reflections | l = −11→12 |
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 atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0862P)2 + 0.0329P] where P = (Fo2 + 2Fc2)/3 |
3036 reflections | (Δ/σ)max < 0.001 |
162 parameters | Δρmax = 0.34 e Å−3 |
1 restraint | Δρmin = −0.16 e Å−3 |
C15H26O2 | V = 686.48 (19) Å3 |
Mr = 238.36 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.9617 (10) Å | µ = 0.07 mm−1 |
b = 12.068 (2) Å | T = 298 K |
c = 9.5909 (15) Å | 0.38 × 0.11 × 0.10 mm |
β = 95.789 (8)° |
Bruker X8 APEX diffractometer | 2698 reflections with I > 2σ(I) |
11541 measured reflections | Rint = 0.031 |
3036 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 1 restraint |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.34 e Å−3 |
3036 reflections | Δρmin = −0.16 e Å−3 |
162 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 | ||
C2 | 0.0588 (3) | 0.50820 (14) | 0.02419 (18) | 0.0314 (4) | |
H2 | 0.1734 | 0.5611 | 0.0000 | 0.038* | |
C4 | 0.2591 (3) | 0.37310 (19) | −0.11371 (19) | 0.0453 (5) | |
H4A | 0.3279 | 0.4210 | −0.1786 | 0.054* | |
H4B | 0.2399 | 0.3005 | −0.1567 | 0.054* | |
C9 | 0.3831 (5) | 0.3909 (3) | 0.4739 (2) | 0.0657 (7) | |
H9A | 0.5201 | 0.3606 | 0.5226 | 0.079* | |
H9B | 0.2942 | 0.4216 | 0.5439 | 0.079* | |
H11 | −0.153 (4) | 0.608 (2) | −0.012 (3) | 0.051 (8)* | |
C1 | 0.1382 (3) | 0.45493 (13) | 0.16735 (17) | 0.0289 (3) | |
H1 | 0.0019 | 0.4272 | 0.2047 | 0.035* | |
C3 | 0.0279 (3) | 0.41938 (15) | −0.09006 (19) | 0.0372 (4) | |
H3 | −0.0630 | 0.3592 | −0.0565 | 0.045* | |
C5 | 0.4180 (3) | 0.36301 (17) | 0.02114 (19) | 0.0395 (4) | |
H5A | 0.5132 | 0.2982 | 0.0162 | 0.047* | |
H5B | 0.5143 | 0.4279 | 0.0323 | 0.047* | |
C6 | 0.2821 (3) | 0.35300 (14) | 0.14433 (17) | 0.0304 (3) | |
C7 | 0.3361 (3) | 0.27224 (16) | 0.2586 (2) | 0.0412 (4) | |
C8 | 0.2506 (4) | 0.2968 (2) | 0.3985 (2) | 0.0545 (6) | |
H8A | 0.2637 | 0.2308 | 0.4564 | 0.065* | |
H8B | 0.0925 | 0.3170 | 0.3840 | 0.065* | |
C10 | 0.4472 (4) | 0.4851 (2) | 0.3774 (2) | 0.0531 (6) | |
H10A | 0.5572 | 0.4567 | 0.3186 | 0.064* | |
H10B | 0.5204 | 0.5431 | 0.4355 | 0.064* | |
C11 | 0.2506 (3) | 0.53852 (15) | 0.28073 (19) | 0.0372 (4) | |
C12 | 0.5456 (4) | 0.2016 (2) | 0.2643 (3) | 0.0612 (6) | |
H12A | 0.5204 | 0.1334 | 0.3119 | 0.092* | |
H12B | 0.6694 | 0.2405 | 0.3140 | 0.092* | |
H12C | 0.5803 | 0.1859 | 0.1708 | 0.092* | |
C13 | −0.0927 (4) | 0.4641 (2) | −0.2266 (2) | 0.0575 (6) | |
H13A | −0.0141 | 0.5281 | −0.2558 | 0.086* | |
H13B | −0.2443 | 0.4842 | −0.2120 | 0.086* | |
H13C | −0.0954 | 0.4080 | −0.2977 | 0.086* | |
C14 | 0.3584 (4) | 0.64005 (19) | 0.2140 (3) | 0.0574 (6) | |
H14A | 0.2429 | 0.6824 | 0.1611 | 0.086* | |
H14B | 0.4661 | 0.6150 | 0.1529 | 0.086* | |
H14C | 0.4329 | 0.6856 | 0.2865 | 0.086* | |
C15 | 0.0719 (4) | 0.5824 (2) | 0.3696 (3) | 0.0636 (7) | |
H15A | 0.1416 | 0.6300 | 0.4416 | 0.095* | |
H15B | 0.0005 | 0.5214 | 0.4118 | 0.095* | |
H15C | −0.0391 | 0.6235 | 0.3113 | 0.095* | |
O1 | −0.1435 (2) | 0.56718 (13) | 0.04280 (17) | 0.0465 (4) | |
O2 | 0.1605 (2) | 0.24617 (10) | 0.14695 (15) | 0.0414 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C2 | 0.0338 (8) | 0.0274 (8) | 0.0338 (9) | −0.0005 (7) | 0.0068 (6) | 0.0023 (7) |
C4 | 0.0540 (11) | 0.0512 (12) | 0.0321 (9) | 0.0069 (9) | 0.0119 (8) | −0.0066 (8) |
C9 | 0.0770 (16) | 0.0825 (18) | 0.0347 (11) | 0.0019 (14) | −0.0090 (10) | 0.0007 (12) |
C1 | 0.0297 (7) | 0.0277 (7) | 0.0300 (8) | −0.0025 (6) | 0.0062 (6) | −0.0001 (6) |
C3 | 0.0429 (10) | 0.0379 (9) | 0.0304 (9) | −0.0010 (7) | 0.0020 (7) | −0.0009 (7) |
C5 | 0.0379 (9) | 0.0398 (9) | 0.0419 (10) | 0.0050 (8) | 0.0100 (7) | −0.0051 (8) |
C6 | 0.0321 (7) | 0.0265 (7) | 0.0317 (8) | −0.0036 (6) | −0.0003 (6) | −0.0027 (7) |
C7 | 0.0462 (10) | 0.0351 (10) | 0.0403 (10) | −0.0033 (8) | −0.0060 (8) | 0.0039 (8) |
C8 | 0.0599 (13) | 0.0623 (14) | 0.0407 (11) | −0.0036 (11) | 0.0022 (9) | 0.0197 (10) |
C10 | 0.0487 (11) | 0.0572 (14) | 0.0514 (13) | −0.0088 (9) | −0.0045 (9) | −0.0138 (10) |
C11 | 0.0398 (9) | 0.0374 (9) | 0.0347 (9) | −0.0056 (7) | 0.0052 (7) | −0.0098 (7) |
C12 | 0.0595 (14) | 0.0520 (13) | 0.0681 (15) | 0.0150 (11) | −0.0130 (11) | 0.0080 (11) |
C13 | 0.0698 (14) | 0.0646 (14) | 0.0352 (11) | 0.0089 (12) | −0.0088 (9) | −0.0009 (10) |
C14 | 0.0689 (14) | 0.0398 (11) | 0.0640 (14) | −0.0125 (11) | 0.0086 (11) | −0.0075 (10) |
C15 | 0.0596 (13) | 0.0766 (17) | 0.0561 (14) | 0.0007 (12) | 0.0141 (11) | −0.0262 (13) |
O1 | 0.0504 (8) | 0.0417 (8) | 0.0490 (9) | 0.0166 (6) | 0.0121 (6) | 0.0105 (7) |
O2 | 0.0490 (8) | 0.0270 (6) | 0.0459 (7) | −0.0068 (5) | −0.0067 (6) | 0.0019 (6) |
C2—O1 | 1.427 (2) | C7—C12 | 1.508 (3) |
C2—C3 | 1.531 (2) | C7—C8 | 1.512 (3) |
C2—C1 | 1.546 (2) | C8—H8A | 0.9700 |
C2—H2 | 0.9800 | C8—H8B | 0.9700 |
C4—C3 | 1.526 (3) | C10—C11 | 1.558 (3) |
C4—C5 | 1.529 (3) | C10—H10A | 0.9700 |
C4—H4A | 0.9700 | C10—H10B | 0.9700 |
C4—H4B | 0.9700 | C11—C15 | 1.525 (3) |
C9—C8 | 1.523 (4) | C11—C14 | 1.552 (3) |
C9—C10 | 1.539 (4) | C12—H12A | 0.9600 |
C9—H9A | 0.9700 | C12—H12B | 0.9600 |
C9—H9B | 0.9700 | C12—H12C | 0.9600 |
C1—C6 | 1.528 (2) | C13—H13A | 0.9600 |
C1—C11 | 1.582 (2) | C13—H13B | 0.9600 |
C1—H1 | 0.9800 | C13—H13C | 0.9600 |
C3—C13 | 1.527 (3) | C14—H14A | 0.9600 |
C3—H3 | 0.9800 | C14—H14B | 0.9600 |
C5—C6 | 1.503 (2) | C14—H14C | 0.9600 |
C5—H5A | 0.9700 | C15—H15A | 0.9600 |
C5—H5B | 0.9700 | C15—H15B | 0.9600 |
C6—C7 | 1.478 (3) | C15—H15C | 0.9600 |
C6—O2 | 1.481 (2) | O1—H11 | 0.72 (3) |
C7—O2 | 1.455 (2) | ||
O1—C2—C3 | 113.36 (15) | C6—C7—C8 | 117.44 (17) |
O1—C2—C1 | 106.45 (14) | C12—C7—C8 | 115.52 (19) |
C3—C2—C1 | 110.40 (13) | C7—C8—C9 | 111.26 (19) |
O1—C2—H2 | 108.8 | C7—C8—H8A | 109.4 |
C3—C2—H2 | 108.8 | C9—C8—H8A | 109.4 |
C1—C2—H2 | 108.8 | C7—C8—H8B | 109.4 |
C3—C4—C5 | 113.30 (14) | C9—C8—H8B | 109.4 |
C3—C4—H4A | 108.9 | H8A—C8—H8B | 108.0 |
C5—C4—H4A | 108.9 | C9—C10—C11 | 116.50 (19) |
C3—C4—H4B | 108.9 | C9—C10—H10A | 108.2 |
C5—C4—H4B | 108.9 | C11—C10—H10A | 108.2 |
H4A—C4—H4B | 107.7 | C9—C10—H10B | 108.2 |
C8—C9—C10 | 114.41 (18) | C11—C10—H10B | 108.2 |
C8—C9—H9A | 108.7 | H10A—C10—H10B | 107.3 |
C10—C9—H9A | 108.7 | C15—C11—C14 | 107.35 (18) |
C8—C9—H9B | 108.7 | C15—C11—C10 | 109.69 (18) |
C10—C9—H9B | 108.7 | C14—C11—C10 | 104.72 (17) |
H9A—C9—H9B | 107.6 | C15—C11—C1 | 109.53 (15) |
C6—C1—C2 | 109.41 (13) | C14—C11—C1 | 112.59 (15) |
C6—C1—C11 | 114.05 (14) | C10—C11—C1 | 112.74 (15) |
C2—C1—C11 | 114.57 (14) | C7—C12—H12A | 109.5 |
C6—C1—H1 | 106.0 | C7—C12—H12B | 109.5 |
C2—C1—H1 | 106.0 | H12A—C12—H12B | 109.5 |
C11—C1—H1 | 106.0 | C7—C12—H12C | 109.5 |
C4—C3—C13 | 110.86 (16) | H12A—C12—H12C | 109.5 |
C4—C3—C2 | 108.51 (15) | H12B—C12—H12C | 109.5 |
C13—C3—C2 | 112.26 (17) | C3—C13—H13A | 109.5 |
C4—C3—H3 | 108.4 | C3—C13—H13B | 109.5 |
C13—C3—H3 | 108.4 | H13A—C13—H13B | 109.5 |
C2—C3—H3 | 108.4 | C3—C13—H13C | 109.5 |
C6—C5—C4 | 109.51 (14) | H13A—C13—H13C | 109.5 |
C6—C5—H5A | 109.8 | H13B—C13—H13C | 109.5 |
C4—C5—H5A | 109.8 | C11—C14—H14A | 109.5 |
C6—C5—H5B | 109.8 | C11—C14—H14B | 109.5 |
C4—C5—H5B | 109.8 | H14A—C14—H14B | 109.5 |
H5A—C5—H5B | 108.2 | C11—C14—H14C | 109.5 |
C7—C6—O2 | 58.92 (11) | H14A—C14—H14C | 109.5 |
C7—C6—C5 | 122.77 (16) | H14B—C14—H14C | 109.5 |
O2—C6—C5 | 112.77 (14) | C11—C15—H15A | 109.5 |
C7—C6—C1 | 120.48 (15) | C11—C15—H15B | 109.5 |
O2—C6—C1 | 114.54 (12) | H15A—C15—H15B | 109.5 |
C5—C6—C1 | 113.81 (14) | C11—C15—H15C | 109.5 |
O2—C7—C6 | 60.64 (11) | H15A—C15—H15C | 109.5 |
O2—C7—C12 | 115.87 (18) | H15B—C15—H15C | 109.5 |
C6—C7—C12 | 121.17 (19) | C2—O1—H11 | 105 (2) |
O2—C7—C8 | 114.42 (17) | C7—O2—C6 | 60.45 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O2i | 0.72 (3) | 2.11 (3) | 2.820 (2) | 171 (3) |
Symmetry code: (i) −x, y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H11···O2i | 0.72 (3) | 2.11 (3) | 2.820 (2) | 171 (3) |
Symmetry code: (i) −x, y+1/2, −z. |
Acknowledgements
The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
This work is a part of our ongoing program concerning the valorization of the most abundant essential oils in Morocco, such as Cedrus atlantica. This oil is made up mainly (75%) of bicyclic sesquiterpene hydrocarbons, among which is found the compound β-himachalene (El Haib et al., 2011). The reactivity of this sesquiterpene and its derivatives has been studied extensively by our team in order to prepare new products having biological properties (El Jamili et al., 2002; Benharref et al., 2013; Ourhriss et al., 2013). Indeed, these compounds were tested, using the food poisoning technique, for their potential antifungal activity against phytopathogen Botrytis cinerea (Daoubi et al., 2004). The molecule of the title compound (Fig.1) is built up from two fused six- and seven-membered rings, both rings have a twist-boat conformation as indicated by the total puckering amplitude QT = 0.7821 (19) Å and spherical polar angle θ = 92.53 (15)° with ϕ = 272.91 (14)°, for the six-membered ring, and QT = 1.1479 (21), θ = 87.76 (10), ϕ2 = -148.25 (21), ϕ3 = 27.36 (3) for the seven-membered ring (Cremer & Pople, 1975). In the crystal, O—H···O hydrogen bonds links the molecules into zigzag chains running along the b axis (Table 1, Fig. 1).