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organic compounds
(1S,2R,8R)-2,2-Dichloro-3,7,7,10-tetramethyltricyclo[6.4.0.01,3]dodec-10-en-9-one
aLaboratoire de Chimie Biomoléculaires, Substances Naturelles et Réactivité, URAC16,Faculté des Sciences Semlalia, BP 2390 Bd My Abdellah, 40000 Marrakech, Morocco, and bLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Avenue Ibn Battouta BP 1014 Rabat, Morocco
*Correspondence e-mail: abenharref@yahoo.fr
The title compound, C16H22Cl2O, was synthesized from β-himachalene, which was isolated from essential oil of the Atlas cedar (cedrus atlantica). The contains two independent molecules, in each of which the six-membered ring shows a half-chair conformation, whereas the seven-membered ring displays a boat conformation. The dihedral angle between the two rings is slightly different in the two molecules [63.22 (13) and 61.81 (14)°].
Related literature
For the isolation of β-himachalene, see: Joseph & Dev (1968); Plattier & Teiseire (1974
). For the reactivity of this sesquiterpene, see: Lassaba et al. (1998
); Chekroun et al. (2000
); El Jamili et al. (2002
); Sbai et al. (2002
); Dakir et al. (2004
). For its biological activity, see: Daoubi et al. (2004
).
Experimental
Crystal data
|
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, 1997
); software used to prepare material for publication: WinGX (Farrugia, 1999
).
Supporting information
https://doi.org/10.1107/S1600536810040213/im2235sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810040213/im2235Isup2.hkl
A solution is prepared by bubbling gaseous hydrochloric acid into 40 ml of chloroform for 1 minute. Then 1 g (3.30 mmol) of (1S,3R,8S,9S,10R)-2,2-dichloro-9,10-epoxy-3,7,7,10-tetramethyltricyclo[6.4.0.01,3]dodecane (X) dissolved in 20 ml of chloroform, is added to this solution and the resulting mixture is stirred for 1 h. After evaporation of the solvent and
of the residue obtained on a column of silica gel, using as hexane-ethyl acetate (95/ 5), the corresponding enol is isolated (yield: 0.6 g, 1.98 mmol, 60%). A solution of the enol (0.5 g, 1.65 mmol) in dichloromethane (20 ml) was added to a suspention of the complex (CrO3: pyridine) (10 mmol) in another 45 ml of dichloromethane. The reaction mixture was stirred at room temperature for 1 h, then filtered through an alumina column. After evaporation of the solvent, the title compound, (1S,2R,8R)-2,2-Dichloro-3,7,7,10-tetramethyl-tricyclo[6.4.0.01,3]dodec-10-en-9-one, is obtained (0.35 g, 70%). Crystals suitable for X-ray analysis were produced by recrystallization from n-pentane.All H atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl),0.97 Å (methylene), 0.98Å (methine) with Uiso(H) = 1.2Ueq (methylene, methine) or Uiso(H) = 1.5Ueq (methyl).
The essential oil of the Atlas cedar (cedrus atlantica) consists mainly (50%) of a bicyclic hydrocarbon sesquiterpene called β-himachalene (Joseph & Dev 1968; Plattier & Teiseire 1974). The reactivity of this sesquiterpene has been studied extensively by our team in order to prepare new products having biological proprieties (Lassaba et al., 1998; Chekroun et al., 2000; El Jamili et al., 2002; Sbai et al., 2002; Dakir et al., 2004). Indeed, these compounds were tested, using the food poisoning technique, for their potential antifungal activity against phytopathogen Botrytis cinerea (Daoubi et al., 2004). Thus the action of one equivalent of dichlorocarbene, generated in situ from chloroform and in the presence of sodium hydroxide as base and n-benzyltriethylammonium chloride as catalyst, followed by epoxydation with m-chloroperbenzoic acid (m-CPBA) gives a mixture of two diasteroisomers:(1S,3R,8S,9S,10R)-2,2-dichloro-9,10-epoxy-3,7,7,10-tetramethyltricyclo[6.4.0.01,3]dodecane (X, 70%) and (1S,3R,8S,9R,10S)-2,2-dichloro-9,10-epoxy-3,7,7,10-tetramethyltricyclo[6.4.0.01,3]dodecane (Y, 30%) (Sbai et al., 2002). By treatment of the majority isomer (X) with hydrochloric acid (see experimental) we obtained the title compound in 70% yield. The structure of (I) was established by 1H and 13C NMR and confirmed by its single crystal X-ray structure. The contains two crystallographically independent molecules (Fig.1). Each molecule is built up from two fused six and seven-membered rings with the dichlorocyclopropyl ring at positions 1 and 2 in α-configuration. The six-membered ring shows a half chair conformation, whereas the seven-membered ring displays a boat conformation. In the first molecule (C1 to C16), the dihedral angle between the rings is 63.22 (13)°. The corresponding value in the second molecule (C17 to C31) is 61.81 (14)°. Owing to the presence of the Cl atoms, the could be fully confirmed to be (1S,2R,8R) for both molecules (Flack & Bernardinelli, 2000).
For the isolation of β-himachalene, see: Joseph & Dev (1968); Plattier & Teiseire (1974). For the reactivity of this sesquiterpene, see: Lassaba et al. (1998); Chekroun et al. (2000); El Jamili et al.(2002); Sbai et al. (2002); Dakir et al. (2004). For its biological activity, see: Daoubi et al. (2004).
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: SHELXS97 (Sheldrick,2008); molecular graphics: ORTEP-3 for Windows (Farrugia,1997); software used to prepare material for publication: WinGX (Farrugia, 1999).C16H22Cl2O | F(000) = 640 |
Mr = 301.24 | Dx = 1.252 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 11524 reflections |
a = 6.6680 (7) Å | θ = 2.3–28.2° |
b = 18.7760 (16) Å | µ = 0.40 mm−1 |
c = 12.7696 (12) Å | T = 298 K |
β = 90.430 (3)° | Prism, colourless |
V = 1598.7 (3) Å3 | 0.27 × 0.18 × 0.12 mm |
Z = 4 |
Bruker X8 APEXII CCD area-detector diffractometer | 4348 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.031 |
Graphite monochromator | θmax = 28.2°, θmin = 2.7° |
φ and ω scans | h = −8→8 |
11524 measured reflections | k = −16→24 |
5817 independent reflections | l = −14→17 |
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)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.0451P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max < 0.001 |
5817 reflections | Δρmax = 0.17 e Å−3 |
351 parameters | Δρmin = −0.17 e Å−3 |
1 restraint | Absolute structure: Flack & Bernardinelli (2000), 1791 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.01 (5) |
C16H22Cl2O | V = 1598.7 (3) Å3 |
Mr = 301.24 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.6680 (7) Å | µ = 0.40 mm−1 |
b = 18.7760 (16) Å | T = 298 K |
c = 12.7696 (12) Å | 0.27 × 0.18 × 0.12 mm |
β = 90.430 (3)° |
Bruker X8 APEXII CCD area-detector diffractometer | 4348 reflections with I > 2σ(I) |
11524 measured reflections | Rint = 0.031 |
5817 independent reflections |
R[F2 > 2σ(F2)] = 0.039 | H-atom parameters constrained |
wR(F2) = 0.094 | Δρmax = 0.17 e Å−3 |
S = 1.00 | Δρmin = −0.17 e Å−3 |
5817 reflections | Absolute structure: Flack & Bernardinelli (2000), 1791 Friedel pairs |
351 parameters | Absolute structure parameter: 0.01 (5) |
1 restraint |
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. |
x | y | z | Uiso*/Ueq | ||
C4 | 0.2648 (4) | 0.51700 (18) | 0.1518 (2) | 0.0665 (8) | |
H4 | 0.3713 | 0.5344 | 0.1916 | 0.080* | |
C5 | 0.3032 (4) | 0.50170 (17) | 0.0397 (2) | 0.0566 (7) | |
H5A | 0.3645 | 0.4551 | 0.0335 | 0.068* | |
H5B | 0.3967 | 0.5366 | 0.0125 | 0.068* | |
C6 | 0.1141 (4) | 0.50357 (13) | −0.02434 (19) | 0.0428 (5) | |
C7 | 0.1190 (4) | 0.50653 (15) | −0.1455 (2) | 0.0555 (7) | |
C13 | 0.3194 (5) | 0.5040 (2) | −0.2006 (3) | 0.0842 (11) | |
H13A | 0.3063 | 0.5251 | −0.2688 | 0.126* | |
H13B | 0.3615 | 0.4553 | −0.2077 | 0.126* | |
H13C | 0.4173 | 0.5298 | −0.1603 | 0.126* | |
C29 | 0.7542 (5) | 0.3406 (2) | 0.3751 (3) | 0.0802 (10) | |
H29A | 0.7532 | 0.3825 | 0.3320 | 0.120* | |
H29B | 0.7934 | 0.3003 | 0.3338 | 0.120* | |
H29C | 0.8478 | 0.3469 | 0.4318 | 0.120* | |
C30 | 0.1340 (6) | 0.1455 (2) | 0.4271 (3) | 0.1001 (13) | |
H30A | 0.0623 | 0.1353 | 0.4903 | 0.150* | |
H30B | 0.1376 | 0.1036 | 0.3841 | 0.150* | |
H30C | 0.0677 | 0.1832 | 0.3898 | 0.150* | |
C32 | 0.4841 (4) | 0.36421 (13) | 0.51889 (19) | 0.0483 (6) | |
Cl2 | 0.23340 (15) | 0.64403 (4) | −0.07935 (7) | 0.0867 (3) | |
Cl3 | 0.24108 (11) | 0.40022 (3) | 0.53257 (6) | 0.0636 (2) | |
Cl4 | 0.65593 (14) | 0.42095 (4) | 0.58207 (7) | 0.0779 (2) | |
C1 | −0.0602 (3) | 0.46308 (12) | 0.02462 (19) | 0.0401 (5) | |
H1 | −0.1815 | 0.4787 | −0.0126 | 0.048* | |
C2 | −0.0857 (4) | 0.48562 (13) | 0.1377 (2) | 0.0478 (6) | |
C3 | 0.0909 (4) | 0.50787 (16) | 0.1996 (2) | 0.0577 (7) | |
C8 | −0.0460 (5) | 0.46708 (15) | −0.2027 (2) | 0.0635 (8) | |
H8A | −0.0446 | 0.4806 | −0.2760 | 0.076* | |
H8B | −0.1744 | 0.4812 | −0.1742 | 0.076* | |
C9 | −0.0246 (6) | 0.38591 (16) | −0.1941 (2) | 0.0753 (9) | |
H9A | −0.1549 | 0.3645 | −0.2070 | 0.090* | |
H9B | 0.0644 | 0.3698 | −0.2490 | 0.090* | |
C10 | 0.0552 (5) | 0.35865 (15) | −0.0899 (2) | 0.0681 (8) | |
H10A | 0.1938 | 0.3738 | −0.0837 | 0.082* | |
H10B | 0.0560 | 0.3070 | −0.0933 | 0.082* | |
C11 | −0.0502 (4) | 0.37973 (13) | 0.0114 (2) | 0.0476 (6) | |
C12 | 0.0569 (6) | 0.52838 (19) | 0.3121 (2) | 0.0791 (10) | |
H12A | 0.1817 | 0.5263 | 0.3499 | 0.119* | |
H12B | −0.0371 | 0.4960 | 0.3430 | 0.119* | |
H12C | 0.0043 | 0.5759 | 0.3151 | 0.119* | |
C14 | −0.2671 (5) | 0.35177 (17) | 0.0103 (3) | 0.0793 (10) | |
H14A | −0.2660 | 0.3008 | 0.0045 | 0.119* | |
H14B | −0.3383 | 0.3718 | −0.0483 | 0.119* | |
H14C | −0.3322 | 0.3653 | 0.0741 | 0.119* | |
C15 | 0.0620 (5) | 0.34352 (16) | 0.1020 (3) | 0.0709 (9) | |
H15A | 0.0584 | 0.2928 | 0.0925 | 0.106* | |
H15B | −0.0008 | 0.3557 | 0.1670 | 0.106* | |
H15C | 0.1989 | 0.3594 | 0.1032 | 0.106* | |
C16 | 0.0640 (4) | 0.57190 (14) | −0.0831 (2) | 0.0545 (7) | |
C17 | 0.3373 (3) | 0.23635 (12) | 0.52663 (18) | 0.0416 (5) | |
H17 | 0.2229 | 0.2643 | 0.5009 | 0.050* | |
C18 | 0.2929 (4) | 0.21847 (13) | 0.6403 (2) | 0.0491 (6) | |
C19 | 0.4595 (4) | 0.21347 (15) | 0.7164 (2) | 0.0566 (7) | |
C20 | 0.6448 (4) | 0.23164 (15) | 0.6869 (2) | 0.0541 (7) | |
H20 | 0.7473 | 0.2279 | 0.7364 | 0.065* | |
C21 | 0.6985 (4) | 0.25743 (14) | 0.5803 (2) | 0.0504 (6) | |
H21A | 0.7596 | 0.2188 | 0.5415 | 0.060* | |
H21B | 0.7965 | 0.2954 | 0.5867 | 0.060* | |
C22 | 0.5185 (4) | 0.28455 (12) | 0.51998 (19) | 0.0394 (5) | |
C23 | 0.5449 (4) | 0.32811 (15) | 0.41890 (19) | 0.0503 (6) | |
C24 | 0.3892 (5) | 0.31700 (17) | 0.3332 (2) | 0.0620 (8) | |
H24A | 0.4055 | 0.3534 | 0.2801 | 0.074* | |
H24B | 0.2564 | 0.3223 | 0.3627 | 0.074* | |
C25 | 0.4058 (6) | 0.2439 (2) | 0.2822 (2) | 0.0831 (10) | |
H25A | 0.5018 | 0.2470 | 0.2256 | 0.100* | |
H25B | 0.2768 | 0.2320 | 0.2513 | 0.100* | |
C26 | 0.4694 (5) | 0.18318 (19) | 0.3547 (3) | 0.0788 (10) | |
H26A | 0.6073 | 0.1919 | 0.3757 | 0.095* | |
H26B | 0.4690 | 0.1398 | 0.3135 | 0.095* | |
C27 | 0.3494 (4) | 0.16840 (15) | 0.4547 (2) | 0.0612 (8) | |
C28 | 0.4103 (5) | 0.1891 (2) | 0.8254 (3) | 0.0821 (10) | |
H28A | 0.5294 | 0.1903 | 0.8681 | 0.123* | |
H28B | 0.3590 | 0.1414 | 0.8230 | 0.123* | |
H28C | 0.3112 | 0.2201 | 0.8549 | 0.123* | |
C31 | 0.4526 (6) | 0.10533 (17) | 0.5119 (3) | 0.0908 (11) | |
H31A | 0.5875 | 0.1184 | 0.5304 | 0.136* | |
H31B | 0.4548 | 0.0646 | 0.4665 | 0.136* | |
H31C | 0.3795 | 0.0940 | 0.5742 | 0.136* | |
O1 | −0.2520 (3) | 0.48319 (13) | 0.17818 (16) | 0.0732 (6) | |
O2 | 0.1224 (3) | 0.20740 (13) | 0.66801 (17) | 0.0771 (6) | |
Cl1 | −0.18216 (13) | 0.60662 (4) | −0.08502 (7) | 0.0734 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C4 | 0.0487 (17) | 0.085 (2) | 0.065 (2) | −0.0084 (15) | −0.0153 (14) | −0.0067 (17) |
C5 | 0.0387 (14) | 0.0655 (18) | 0.0656 (18) | −0.0037 (12) | −0.0004 (12) | −0.0059 (14) |
C6 | 0.0402 (13) | 0.0434 (13) | 0.0447 (14) | −0.0043 (10) | −0.0006 (11) | −0.0034 (11) |
C7 | 0.0677 (18) | 0.0501 (15) | 0.0489 (16) | −0.0119 (13) | 0.0092 (13) | −0.0005 (12) |
C13 | 0.092 (3) | 0.089 (3) | 0.072 (2) | −0.019 (2) | 0.0332 (19) | −0.0136 (19) |
C29 | 0.072 (2) | 0.100 (3) | 0.070 (2) | −0.0123 (19) | 0.0127 (17) | 0.0220 (19) |
C30 | 0.077 (2) | 0.087 (3) | 0.137 (3) | −0.019 (2) | −0.014 (2) | −0.052 (3) |
C32 | 0.0542 (15) | 0.0398 (13) | 0.0506 (16) | 0.0004 (11) | −0.0125 (12) | 0.0009 (11) |
Cl2 | 0.1082 (7) | 0.0573 (5) | 0.0947 (6) | −0.0378 (5) | 0.0078 (5) | −0.0006 (4) |
Cl3 | 0.0704 (5) | 0.0544 (4) | 0.0658 (4) | 0.0229 (3) | −0.0103 (3) | −0.0051 (3) |
Cl4 | 0.0927 (6) | 0.0486 (4) | 0.0918 (6) | −0.0169 (4) | −0.0318 (4) | −0.0002 (4) |
C1 | 0.0353 (13) | 0.0399 (13) | 0.0449 (14) | 0.0020 (10) | −0.0076 (10) | 0.0039 (11) |
C2 | 0.0454 (15) | 0.0471 (14) | 0.0511 (16) | 0.0094 (11) | 0.0035 (12) | 0.0059 (12) |
C3 | 0.0539 (18) | 0.0667 (18) | 0.0522 (16) | 0.0042 (14) | −0.0065 (13) | −0.0101 (14) |
C8 | 0.089 (2) | 0.0588 (17) | 0.0430 (15) | −0.0148 (15) | −0.0073 (14) | −0.0008 (13) |
C9 | 0.118 (3) | 0.0553 (18) | 0.0527 (17) | −0.0167 (18) | −0.0016 (17) | −0.0117 (14) |
C10 | 0.091 (2) | 0.0446 (16) | 0.069 (2) | 0.0051 (15) | −0.0035 (16) | −0.0075 (14) |
C11 | 0.0488 (15) | 0.0406 (13) | 0.0532 (15) | −0.0014 (11) | −0.0020 (12) | 0.0025 (11) |
C12 | 0.105 (3) | 0.080 (2) | 0.0529 (18) | −0.003 (2) | −0.0018 (17) | −0.0074 (16) |
C14 | 0.075 (2) | 0.0495 (17) | 0.114 (3) | −0.0145 (15) | −0.0048 (19) | 0.0074 (17) |
C15 | 0.081 (2) | 0.0552 (17) | 0.076 (2) | 0.0137 (15) | −0.0104 (17) | 0.0120 (15) |
C16 | 0.0626 (18) | 0.0459 (14) | 0.0549 (17) | −0.0149 (13) | −0.0024 (13) | −0.0026 (13) |
C17 | 0.0348 (13) | 0.0408 (13) | 0.0490 (15) | 0.0067 (10) | −0.0050 (10) | −0.0034 (11) |
C18 | 0.0430 (15) | 0.0421 (14) | 0.0624 (17) | 0.0073 (11) | 0.0050 (12) | 0.0054 (12) |
C19 | 0.0551 (17) | 0.0587 (17) | 0.0559 (17) | 0.0108 (13) | −0.0002 (13) | 0.0135 (13) |
C20 | 0.0510 (16) | 0.0544 (15) | 0.0566 (17) | 0.0087 (12) | −0.0141 (13) | 0.0066 (13) |
C21 | 0.0460 (15) | 0.0466 (14) | 0.0584 (17) | 0.0029 (11) | −0.0054 (12) | 0.0061 (12) |
C22 | 0.0378 (13) | 0.0395 (12) | 0.0410 (13) | 0.0040 (10) | −0.0019 (10) | −0.0007 (10) |
C23 | 0.0494 (16) | 0.0582 (16) | 0.0433 (14) | 0.0008 (12) | −0.0001 (12) | 0.0077 (13) |
C24 | 0.070 (2) | 0.0738 (19) | 0.0416 (15) | 0.0087 (15) | −0.0054 (13) | 0.0035 (15) |
C25 | 0.102 (3) | 0.098 (3) | 0.0487 (18) | 0.011 (2) | −0.0075 (17) | −0.0172 (18) |
C26 | 0.088 (2) | 0.073 (2) | 0.076 (2) | 0.0114 (18) | 0.0056 (18) | −0.0394 (18) |
C27 | 0.0563 (17) | 0.0455 (15) | 0.082 (2) | −0.0012 (12) | −0.0020 (15) | −0.0182 (15) |
C28 | 0.090 (2) | 0.090 (3) | 0.066 (2) | 0.015 (2) | 0.0108 (18) | 0.0236 (19) |
C31 | 0.097 (3) | 0.0443 (17) | 0.131 (3) | 0.0114 (18) | 0.003 (2) | −0.010 (2) |
O1 | 0.0502 (12) | 0.1049 (17) | 0.0647 (13) | 0.0081 (11) | 0.0127 (10) | 0.0001 (12) |
O2 | 0.0439 (12) | 0.0959 (17) | 0.0917 (16) | 0.0044 (11) | 0.0137 (10) | 0.0280 (13) |
Cl1 | 0.0823 (6) | 0.0530 (4) | 0.0846 (5) | 0.0118 (4) | −0.0146 (4) | 0.0132 (4) |
C4—C3 | 1.326 (4) | C11—C15 | 1.532 (4) |
C4—C5 | 1.484 (4) | C11—C14 | 1.538 (4) |
C4—H4 | 0.9300 | C12—H12A | 0.9600 |
C5—C6 | 1.498 (4) | C12—H12B | 0.9600 |
C5—H5A | 0.9700 | C12—H12C | 0.9600 |
C5—H5B | 0.9700 | C14—H14A | 0.9600 |
C6—C16 | 1.522 (4) | C14—H14B | 0.9600 |
C6—C1 | 1.527 (3) | C14—H14C | 0.9600 |
C6—C7 | 1.549 (4) | C15—H15A | 0.9600 |
C7—C16 | 1.510 (4) | C15—H15B | 0.9600 |
C7—C8 | 1.510 (4) | C15—H15C | 0.9600 |
C7—C13 | 1.516 (4) | C16—Cl1 | 1.766 (3) |
C13—H13A | 0.9600 | C17—C22 | 1.513 (3) |
C13—H13B | 0.9600 | C17—C18 | 1.521 (4) |
C13—H13C | 0.9600 | C17—C27 | 1.574 (3) |
C29—C23 | 1.526 (4) | C17—H17 | 0.9800 |
C29—H29A | 0.9600 | C18—O2 | 1.211 (3) |
C29—H29B | 0.9600 | C18—C19 | 1.473 (4) |
C29—H29C | 0.9600 | C19—C20 | 1.339 (4) |
C30—C27 | 1.537 (4) | C19—C28 | 1.505 (4) |
C30—H30A | 0.9600 | C20—C21 | 1.491 (4) |
C30—H30B | 0.9600 | C20—H20 | 0.9300 |
C30—H30C | 0.9600 | C21—C22 | 1.509 (3) |
C32—C23 | 1.504 (4) | C21—H21A | 0.9700 |
C32—C22 | 1.513 (3) | C21—H21B | 0.9700 |
C32—Cl4 | 1.756 (3) | C22—C23 | 1.539 (3) |
C32—Cl3 | 1.766 (3) | C23—C24 | 1.517 (4) |
Cl2—C16 | 1.764 (3) | C24—C25 | 1.523 (5) |
C1—C2 | 1.515 (4) | C24—H24A | 0.9700 |
C1—C11 | 1.576 (3) | C24—H24B | 0.9700 |
C1—H1 | 0.9800 | C25—C26 | 1.527 (5) |
C2—O1 | 1.228 (3) | C25—H25A | 0.9700 |
C2—C3 | 1.474 (4) | C25—H25B | 0.9700 |
C3—C12 | 1.506 (4) | C26—C27 | 1.537 (5) |
C8—C9 | 1.535 (4) | C26—H26A | 0.9700 |
C8—H8A | 0.9700 | C26—H26B | 0.9700 |
C8—H8B | 0.9700 | C27—C31 | 1.549 (5) |
C9—C10 | 1.519 (4) | C28—H28A | 0.9600 |
C9—H9A | 0.9700 | C28—H28B | 0.9600 |
C9—H9B | 0.9700 | C28—H28C | 0.9600 |
C10—C11 | 1.529 (4) | C31—H31A | 0.9600 |
C10—H10A | 0.9700 | C31—H31B | 0.9600 |
C10—H10B | 0.9700 | C31—H31C | 0.9600 |
C3—C4—C5 | 125.3 (3) | C11—C14—H14A | 109.5 |
C3—C4—H4 | 117.4 | C11—C14—H14B | 109.5 |
C5—C4—H4 | 117.4 | H14A—C14—H14B | 109.5 |
C4—C5—C6 | 111.8 (2) | C11—C14—H14C | 109.5 |
C4—C5—H5A | 109.3 | H14A—C14—H14C | 109.5 |
C6—C5—H5A | 109.3 | H14B—C14—H14C | 109.5 |
C4—C5—H5B | 109.3 | C11—C15—H15A | 109.5 |
C6—C5—H5B | 109.3 | C11—C15—H15B | 109.5 |
H5A—C5—H5B | 107.9 | H15A—C15—H15B | 109.5 |
C5—C6—C16 | 118.0 (2) | C11—C15—H15C | 109.5 |
C5—C6—C1 | 113.9 (2) | H15A—C15—H15C | 109.5 |
C16—C6—C1 | 117.1 (2) | H15B—C15—H15C | 109.5 |
C5—C6—C7 | 121.5 (2) | C7—C16—C6 | 61.42 (18) |
C16—C6—C7 | 58.90 (17) | C7—C16—Cl2 | 118.7 (2) |
C1—C6—C7 | 116.6 (2) | C6—C16—Cl2 | 119.7 (2) |
C16—C7—C8 | 118.4 (3) | C7—C16—Cl1 | 121.5 (2) |
C16—C7—C13 | 119.3 (3) | C6—C16—Cl1 | 121.25 (19) |
C8—C7—C13 | 113.7 (3) | Cl2—C16—Cl1 | 108.17 (15) |
C16—C7—C6 | 59.67 (17) | C22—C17—C18 | 110.30 (19) |
C8—C7—C6 | 116.4 (2) | C22—C17—C27 | 114.06 (19) |
C13—C7—C6 | 119.2 (3) | C18—C17—C27 | 112.9 (2) |
C7—C13—H13A | 109.5 | C22—C17—H17 | 106.3 |
C7—C13—H13B | 109.5 | C18—C17—H17 | 106.3 |
H13A—C13—H13B | 109.5 | C27—C17—H17 | 106.3 |
C7—C13—H13C | 109.5 | O2—C18—C19 | 120.1 (2) |
H13A—C13—H13C | 109.5 | O2—C18—C17 | 120.4 (2) |
H13B—C13—H13C | 109.5 | C19—C18—C17 | 119.5 (2) |
C23—C29—H29A | 109.5 | C20—C19—C18 | 119.4 (2) |
C23—C29—H29B | 109.5 | C20—C19—C28 | 123.1 (3) |
H29A—C29—H29B | 109.5 | C18—C19—C28 | 117.5 (3) |
C23—C29—H29C | 109.5 | C19—C20—C21 | 124.6 (2) |
H29A—C29—H29C | 109.5 | C19—C20—H20 | 117.7 |
H29B—C29—H29C | 109.5 | C21—C20—H20 | 117.7 |
C27—C30—H30A | 109.5 | C20—C21—C22 | 112.3 (2) |
C27—C30—H30B | 109.5 | C20—C21—H21A | 109.1 |
H30A—C30—H30B | 109.5 | C22—C21—H21A | 109.1 |
C27—C30—H30C | 109.5 | C20—C21—H21B | 109.1 |
H30A—C30—H30C | 109.5 | C22—C21—H21B | 109.1 |
H30B—C30—H30C | 109.5 | H21A—C21—H21B | 107.9 |
C23—C32—C22 | 61.35 (17) | C21—C22—C17 | 113.7 (2) |
C23—C32—Cl4 | 118.95 (19) | C21—C22—C32 | 117.3 (2) |
C22—C32—Cl4 | 119.78 (18) | C17—C22—C32 | 118.1 (2) |
C23—C32—Cl3 | 120.68 (18) | C21—C22—C23 | 120.8 (2) |
C22—C32—Cl3 | 121.13 (18) | C17—C22—C23 | 117.5 (2) |
Cl4—C32—Cl3 | 108.56 (14) | C32—C22—C23 | 59.02 (17) |
C2—C1—C6 | 110.0 (2) | C32—C23—C24 | 119.1 (2) |
C2—C1—C11 | 112.6 (2) | C32—C23—C29 | 119.7 (3) |
C6—C1—C11 | 114.7 (2) | C24—C23—C29 | 112.3 (2) |
C2—C1—H1 | 106.3 | C32—C23—C22 | 59.62 (15) |
C6—C1—H1 | 106.3 | C24—C23—C22 | 116.7 (2) |
C11—C1—H1 | 106.3 | C29—C23—C22 | 120.0 (2) |
O1—C2—C3 | 120.3 (2) | C23—C24—C25 | 112.4 (3) |
O1—C2—C1 | 119.9 (2) | C23—C24—H24A | 109.1 |
C3—C2—C1 | 119.7 (2) | C25—C24—H24A | 109.1 |
C4—C3—C2 | 119.2 (3) | C23—C24—H24B | 109.1 |
C4—C3—C12 | 123.0 (3) | C25—C24—H24B | 109.1 |
C2—C3—C12 | 117.3 (2) | H24A—C24—H24B | 107.9 |
C7—C8—C9 | 112.7 (3) | C24—C25—C26 | 115.7 (3) |
C7—C8—H8A | 109.1 | C24—C25—H25A | 108.3 |
C9—C8—H8A | 109.1 | C26—C25—H25A | 108.3 |
C7—C8—H8B | 109.1 | C24—C25—H25B | 108.3 |
C9—C8—H8B | 109.1 | C26—C25—H25B | 108.3 |
H8A—C8—H8B | 107.8 | H25A—C25—H25B | 107.4 |
C10—C9—C8 | 115.4 (2) | C25—C26—C27 | 119.7 (3) |
C10—C9—H9A | 108.4 | C25—C26—H26A | 107.4 |
C8—C9—H9A | 108.4 | C27—C26—H26A | 107.4 |
C10—C9—H9B | 108.4 | C25—C26—H26B | 107.4 |
C8—C9—H9B | 108.4 | C27—C26—H26B | 107.4 |
H9A—C9—H9B | 107.5 | H26A—C26—H26B | 106.9 |
C9—C10—C11 | 119.6 (3) | C30—C27—C26 | 110.6 (3) |
C9—C10—H10A | 107.4 | C30—C27—C31 | 107.7 (3) |
C11—C10—H10A | 107.4 | C26—C27—C31 | 107.3 (3) |
C9—C10—H10B | 107.4 | C30—C27—C17 | 108.0 (2) |
C11—C10—H10B | 107.4 | C26—C27—C17 | 111.6 (2) |
H10A—C10—H10B | 106.9 | C31—C27—C17 | 111.7 (3) |
C10—C11—C15 | 107.4 (2) | C19—C28—H28A | 109.5 |
C10—C11—C14 | 110.0 (2) | C19—C28—H28B | 109.5 |
C15—C11—C14 | 108.0 (2) | H28A—C28—H28B | 109.5 |
C10—C11—C1 | 111.6 (2) | C19—C28—H28C | 109.5 |
C15—C11—C1 | 112.4 (2) | H28A—C28—H28C | 109.5 |
C14—C11—C1 | 107.4 (2) | H28B—C28—H28C | 109.5 |
C3—C12—H12A | 109.5 | C27—C31—H31A | 109.5 |
C3—C12—H12B | 109.5 | C27—C31—H31B | 109.5 |
H12A—C12—H12B | 109.5 | H31A—C31—H31B | 109.5 |
C3—C12—H12C | 109.5 | C27—C31—H31C | 109.5 |
H12A—C12—H12C | 109.5 | H31A—C31—H31C | 109.5 |
H12B—C12—H12C | 109.5 | H31B—C31—H31C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C16H22Cl2O |
Mr | 301.24 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 298 |
a, b, c (Å) | 6.6680 (7), 18.7760 (16), 12.7696 (12) |
β (°) | 90.430 (3) |
V (Å3) | 1598.7 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.40 |
Crystal size (mm) | 0.27 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Bruker X8 APEXII CCD area-detector |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11524, 5817, 4348 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.094, 1.00 |
No. of reflections | 5817 |
No. of parameters | 351 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.17, −0.17 |
Absolute structure | Flack & Bernardinelli (2000), 1791 Friedel pairs |
Absolute structure parameter | 0.01 (5) |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick,2008), ORTEP-3 for Windows (Farrugia,1997), WinGX (Farrugia, 1999).
Acknowledgements
We thank the National Center of Scientific and Technological Research (CNRST) for its support of our research.
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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.
The essential oil of the Atlas cedar (cedrus atlantica) consists mainly (50%) of a bicyclic hydrocarbon sesquiterpene called β-himachalene (Joseph & Dev 1968; Plattier & Teiseire 1974). The reactivity of this sesquiterpene has been studied extensively by our team in order to prepare new products having biological proprieties (Lassaba et al., 1998; Chekroun et al., 2000; El Jamili et al., 2002; Sbai et al., 2002; Dakir et al., 2004). Indeed, these compounds were tested, using the food poisoning technique, for their potential antifungal activity against phytopathogen Botrytis cinerea (Daoubi et al., 2004). Thus the action of one equivalent of dichlorocarbene, generated in situ from chloroform and in the presence of sodium hydroxide as base and n-benzyltriethylammonium chloride as catalyst, followed by epoxydation with m-chloroperbenzoic acid (m-CPBA) gives a mixture of two diasteroisomers:(1S,3R,8S,9S,10R)-2,2-dichloro-9,10-epoxy-3,7,7,10-tetramethyltricyclo[6.4.0.01,3]dodecane (X, 70%) and (1S,3R,8S,9R,10S)-2,2-dichloro-9,10-epoxy-3,7,7,10-tetramethyltricyclo[6.4.0.01,3]dodecane (Y, 30%) (Sbai et al., 2002). By treatment of the majority isomer (X) with hydrochloric acid (see experimental) we obtained the title compound in 70% yield. The structure of (I) was established by 1H and 13C NMR and confirmed by its single crystal X-ray structure. The asymmetric unit contains two crystallographically independent molecules (Fig.1). Each molecule is built up from two fused six and seven-membered rings with the dichlorocyclopropyl ring at positions 1 and 2 in α-configuration. The six-membered ring shows a half chair conformation, whereas the seven-membered ring displays a boat conformation. In the first molecule (C1 to C16), the dihedral angle between the rings is 63.22 (13)°. The corresponding value in the second molecule (C17 to C31) is 61.81 (14)°. Owing to the presence of the Cl atoms, the absolute configuration could be fully confirmed to be (1S,2R,8R) for both molecules (Flack & Bernardinelli, 2000).