Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020547/cf6019sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020547/cf6019Isup2.hkl |
CCDC reference: 159716
Préparation du (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetraméthyltricyclo[6.4.0.01,3]dodec-9-ène: a une solution du β-himachalène (2 g, 9.7 mmol) dans 60 ml dihexane à 278 K, on ajoute (4 g, 35 mmol) de tertiobutylate de potassium. Le mélange réactionnel est agité pendant 8 h. Après hydrolyse avec 20 ml d'eau la phase organique est extraite à l'éther, lavée à l'eau, séchée puis concentrée. Une chromatographie sur alumine neutre du résidu obtenu donne (1S,3R,8S)-2,2-dichloro-3,7,7,10 - tétraméthyltricyclo[6.4.0.01,3]dodec-9- ène (R = 50%, m.p. = 357–358 K). Préparation du (1S,3S,8S)-3,7,7,10 - tétraméthyltricyclo[6.4.0.01,3]dodec-9-ène: dans un ballon muni d'une ampoule à brome, d'un agitateur magnétique et d'un réfrigérant, on place (1 g, 3.48 mmol) de dérivé dichloré dans 40 ml diéther. On refroidit le tout à 273 K. On ajoute par petites portions (3 g, 0.13 mol) du sodium et goutte à goutte 20 ml d'une solution de méthanol à 2.5% en eau pendant une heure. On laisse agiter pendant trois heures puis on ajoute (1 g, 43 mmol) de sodium et 10 ml de méthanol à 2.5%. Après agitation pendant une nuit, on ajoute un peu d'eau et on extrait à l'éther. La phase organique est séchée et évaporée. Une chromatographie sur gel de silice du mélange réactionnel avec le pentane comme éluant a permis d'obtenir (1S,3S,8S)-3,7,7,10 - tétraméthyltricyclo[6.4.0.01,3]dodec-9-ène avec un rendement de 98%. Epoxydation du (1S,3S,8R)-3,7,7,10 - tétraméthyltricyclo[6,4,0,01,3]dodec-9-ène: dans un ballon de 100 ml contenant (200 mg, 0.917 mmol) de (1S,3S,8S)-3,7,7,10 - tétraméthyltricyclo [6.4.0.01,3]dodec-9-ène solubilisé dans 20 ml de CH2Cl2, on ajoute une quantité stoechiométrique de diacide m-chloroperbenzoique (m-CPBA). Le mélange réactionnel est maintenu sous agitation à 273 K pendant 2 h, puis traité par une solution dihydrogénocarbonate de sodium à 10%. La phase aqueuse est extraite à l'éther. Les phases organiques sont séchées puis concentrées. Une analyse par chromatographie en phase gaseuse du résidu obtenu donne 10% de (1S,3S,8R,9S,10R)-9,10-époxy-3,7,7,10 - tétraméthyltricyclo[6,4,0,01,3]- dodécane et 90% de (1S,3S,8R,9S,10R)-9,10-époxy-3,7,7,10-tetraméthyltricyclo[6,4,0,01,3]- dodécane.
Les données ne contiennent pas de paires de Friedel et nous n'avons pas procédé à la détermination de la structure absolue.
Data collection: KappaCCD Reference Manual(Nonius, 1998); data reduction: DENZO and SCALEPAK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: maXus (Mackay et al., 1999); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: maXus.
Fig. 1. Perspective view of the molecule showing the labelling of the atoms with displacement ellipsoids at the 50% probability level. |
C32H50O | Dx = 1.081 Mg m−3 |
Mr = 450.75 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 18475 reflections |
a = 8.7475 (2) Å | θ = 1.0–25.6° |
b = 15.553 (1) Å | µ = 0.06 mm−1 |
c = 20.359 (1) Å | T = 298 K |
V = 2769.8 (2) Å3 | Cube, colourless |
Z = 4 | 0.30 × 0.25 × 0.20 mm |
F(000) = 1040 |
KappaCCD diffractometer | Rint = 0.074 |
Radiation source: fine-focus sealed tube | θmax = 25.6° |
ϕ scans | h = 0→9 |
3021 measured reflections | k = 0→19 |
2912 independent reflections | l = 0→25 |
2673 reflections with I > 2σ(I) |
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)] = 0.086 | H-atom parameters not refined |
wR(F2) = 0.051 | Weighting scheme based on measured s.u.'s w = 1 / (σ2(Fo2) + 0.03Fo2) |
S = 2.12 | (Δ/σ)max = 0.010 |
2673 reflections | Δρmax = 0.28 e Å−3 |
303 parameters | Δρmin = −0.24 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C32H50O | V = 2769.8 (2) Å3 |
Mr = 450.75 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.7475 (2) Å | µ = 0.06 mm−1 |
b = 15.553 (1) Å | T = 298 K |
c = 20.359 (1) Å | 0.30 × 0.25 × 0.20 mm |
KappaCCD diffractometer | 2673 reflections with I > 2σ(I) |
3021 measured reflections | Rint = 0.074 |
2912 independent reflections |
R[F2 > 2σ(F2)] = 0.086 | 303 parameters |
wR(F2) = 0.051 | H-atom parameters not refined |
S = 2.12 | Δρmax = 0.28 e Å−3 |
2673 reflections | Δρmin = −0.24 e Å−3 |
Geometry. All standard uncertainties (except dihedral angles between l.s. planes) are estimated using the full covariance matrix. The standard uncertainties in cell dimensions are are used in calculating the standard uncertainties of bond distances, angles and torsion angles. Angles between l.s. planes have standard uncertainties calculated from atomic positional standard uncertainties; the errors in cell dimensions are not used in this case. |
Refinement. Refinement on F2. |
x | y | z | Uiso*/Ueq | ||
O17 | −0.73534 (6) | −0.14529 (3) | −0.40254 (3) | 0.0341 (3) | |
C1 | −0.81694 (10) | −0.18121 (5) | −0.34712 (4) | 0.0341 (5) | |
C2 | −0.89274 (10) | −0.11204 (6) | −0.30839 (4) | 0.0411 (5) | |
C3 | −0.78976 (12) | −0.05270 (6) | −0.27318 (5) | 0.0567 (6) | |
C4 | −0.67685 (11) | −0.10328 (5) | −0.22942 (4) | 0.0459 (5) | |
C5 | −0.59038 (9) | −0.16894 (5) | −0.27103 (4) | 0.0340 (5) | |
C6 | −0.69441 (9) | −0.23089 (5) | −0.30846 (4) | 0.0303 (4) | |
C7 | −0.75620 (13) | −0.30778 (6) | −0.26621 (5) | 0.0510 (6) | |
C8 | −0.64418 (15) | −0.33300 (7) | −0.21224 (5) | 0.0734 (8) | |
C9 | −0.48146 (15) | −0.35818 (7) | −0.22953 (6) | 0.0799 (8) | |
C10 | −0.39596 (11) | −0.29190 (7) | −0.26973 (5) | 0.0664 (7) | |
C11 | −0.43368 (10) | −0.19973 (6) | −0.25141 (4) | 0.0477 (6) | |
C12 | −0.45104 (10) | −0.13566 (6) | −0.30738 (5) | 0.0493 (6) | |
C13 | −0.36189 (12) | −0.17081 (7) | −0.18793 (5) | 0.0737 (7) | |
C14 | −0.91127 (15) | −0.29167 (8) | −0.23357 (7) | 0.0988 (9) | |
C15 | −0.77479 (18) | −0.38501 (7) | −0.31241 (6) | 0.1053 (10) | |
C16 | −1.04497 (13) | −0.10479 (7) | −0.30752 (6) | 0.0709 (7) | |
C18 | −0.82963 (10) | −0.11611 (5) | −0.45675 (4) | 0.0381 (5) | |
C19 | −0.79671 (11) | −0.17409 (5) | −0.51411 (4) | 0.0475 (6) | |
C20 | −0.71738 (11) | −0.14999 (6) | −0.56487 (4) | 0.0484 (6) | |
C21 | −0.65299 (12) | −0.06238 (6) | −0.57469 (4) | 0.0505 (6) | |
C22 | −0.64922 (11) | −0.01263 (5) | −0.51085 (4) | 0.0389 (5) | |
C23 | −0.79311 (10) | −0.02068 (5) | −0.47017 (4) | 0.0414 (5) | |
C24 | −0.93145 (12) | 0.03401 (7) | −0.49622 (5) | 0.0595 (7) | |
C25 | −0.87429 (17) | 0.11530 (8) | −0.53165 (6) | 0.0836 (9) | |
C26 | −0.77153 (19) | 0.17864 (7) | −0.49247 (7) | 0.1019 (10) | |
C27 | −0.62358 (17) | 0.13985 (6) | −0.46391 (5) | 0.0825 (8) | |
C28 | −0.55882 (12) | 0.07073 (6) | −0.50791 (5) | 0.0569 (6) | |
C29 | −0.49825 (12) | −0.01039 (6) | −0.47494 (5) | 0.0596 (6) | |
C30 | −0.47792 (15) | 0.10412 (7) | −0.56977 (6) | 0.0857 (8) | |
C31 | −1.02949 (14) | −0.01519 (9) | −0.54698 (6) | 0.0943 (9) | |
C32 | −1.03830 (17) | 0.05483 (9) | −0.43962 (6) | 0.1171 (11) | |
C33 | −0.85137 (15) | −0.26657 (6) | −0.50652 (5) | 0.0765 (8) | |
H1 | −0.89433 | −0.21920 | −0.36372 | 0.0541* | |
H6 | −0.62660 | −0.25959 | −0.33836 | 0.0503* | |
H18 | −0.93523 | −0.12141 | −0.44455 | 0.0581* | |
H20 | −0.69648 | −0.18978 | −0.59976 | 0.0684* | |
H23 | −0.77351 | 0.00361 | −0.42767 | 0.0614* | |
H3A | −0.73256 | −0.02100 | −0.30528 | 0.0767* | |
H3B | −0.84835 | −0.01350 | −0.24688 | 0.0767* | |
H4A | −0.73355 | −0.13178 | −0.19542 | 0.0660* | |
H4B | −0.60465 | −0.06438 | −0.20992 | 0.0660* | |
H8A | −0.69344 | −0.37997 | −0.19015 | 0.0935* | |
H8B | −0.64263 | −0.28365 | −0.18392 | 0.0935* | |
H9A | −0.48782 | −0.41166 | −0.25292 | 0.0999* | |
H9B | −0.42882 | −0.36701 | −0.18871 | 0.0999* | |
H10A | −0.42186 | −0.29830 | −0.31533 | 0.0864* | |
H10B | −0.28810 | −0.30030 | −0.26410 | 0.0860* | |
H12A | −0.40904 | −0.15876 | −0.34718 | 0.0694* | |
H12B | −0.39744 | −0.08396 | −0.29588 | 0.0694* | |
H13A | −0.39269 | −0.11251 | −0.17974 | 0.0938* | |
H13B | −0.39379 | −0.20651 | −0.15203 | 0.0938* | |
H13C | −0.25270 | −0.17330 | −0.19210 | 0.0940* | |
H14A | −0.90197 | −0.24387 | −0.20397 | 0.1191* | |
H14B | −0.98547 | −0.27837 | −0.26677 | 0.1191* | |
H14C | −0.94357 | −0.34167 | −0.20967 | 0.1191* | |
H15A | −0.67839 | −0.39681 | −0.33311 | 0.1254* | |
H15B | −0.80759 | −0.43461 | −0.28821 | 0.1254* | |
H15C | −0.84951 | −0.37141 | −0.34541 | 0.1254* | |
H16A | −1.10617 | −0.14649 | −0.33024 | 0.0910* | |
H16B | −1.09317 | −0.05829 | −0.28442 | 0.0910* | |
H21A | −0.55079 | −0.06698 | −0.59149 | 0.0705* | |
H21B | −0.71549 | −0.03178 | −0.60569 | 0.0705* | |
H25A | −0.96606 | 0.14441 | −0.54484 | 0.1037* | |
H25B | −0.82151 | 0.09465 | −0.56986 | 0.1037* | |
H26A | −0.74493 | 0.22504 | −0.52147 | 0.1219* | |
H26B | −0.83373 | 0.20024 | −0.45727 | 0.1219* | |
H27A | −0.64578 | 0.11415 | −0.42211 | 0.1026* | |
H27B | −0.54748 | 0.18375 | −0.45851 | 0.1026* | |
H29A | −0.48582 | 0.00051 | −0.42884 | 0.0797* | |
H29B | −0.40115 | −0.02509 | −0.49384 | 0.0797* | |
H30A | −0.52952 | 0.15462 | −0.58537 | 0.1057* | |
H30B | −0.37382 | 0.11812 | −0.55948 | 0.1057* | |
H30C | −0.48002 | 0.06062 | −0.60317 | 0.1057* | |
H31A | −0.96728 | −0.02999 | −0.58418 | 0.1143* | |
H31B | −1.06878 | −0.06669 | −0.52718 | 0.1143* | |
H31C | −1.11298 | 0.02031 | −0.56108 | 0.1143* | |
H32A | −0.98109 | 0.08573 | −0.40702 | 0.1372* | |
H32B | −1.12170 | 0.08971 | −0.45471 | 0.1372* | |
H32C | −1.07749 | 0.00273 | −0.42082 | 0.1372* | |
H33A | −0.82507 | −0.29957 | −0.54472 | 0.0965* | |
H33B | −0.80188 | −0.29067 | −0.46862 | 0.0965* | |
H33C | −0.96018 | −0.26777 | −0.50032 | 0.0965* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O17 | 0.0275 (3) | 0.0456 (3) | 0.0292 (3) | 0.0012 (3) | −0.0022 (3) | 0.0066 (3) |
C1 | 0.0309 (5) | 0.0384 (5) | 0.0329 (5) | −0.0077 (4) | −0.0014 (4) | 0.0059 (4) |
C2 | 0.0329 (6) | 0.0495 (6) | 0.0410 (5) | 0.0073 (5) | 0.0048 (4) | 0.0017 (5) |
C3 | 0.0643 (8) | 0.0458 (5) | 0.0600 (7) | 0.0148 (5) | 0.0032 (6) | −0.0111 (5) |
C4 | 0.0517 (6) | 0.0482 (5) | 0.0379 (5) | −0.0028 (5) | −0.0039 (5) | −0.0113 (4) |
C5 | 0.0353 (5) | 0.0420 (5) | 0.0248 (4) | −0.0018 (4) | −0.0008 (4) | 0.0051 (4) |
C6 | 0.0304 (5) | 0.0339 (4) | 0.0266 (4) | 0.0013 (4) | 0.0028 (4) | −0.0009 (4) |
C7 | 0.0628 (7) | 0.0405 (5) | 0.0498 (6) | −0.0070 (5) | −0.0061 (5) | 0.0146 (5) |
C8 | 0.0887 (9) | 0.0699 (7) | 0.0616 (7) | 0.0041 (7) | 0.0012 (6) | 0.0347 (6) |
C9 | 0.0977 (10) | 0.0764 (8) | 0.0657 (8) | 0.0286 (7) | −0.0144 (7) | 0.0150 (7) |
C10 | 0.0468 (7) | 0.1031 (9) | 0.0494 (6) | 0.0355 (6) | 0.0019 (5) | 0.0087 (6) |
C11 | 0.0355 (6) | 0.0772 (7) | 0.0304 (5) | 0.0001 (5) | −0.0031 (4) | 0.0026 (5) |
C12 | 0.0292 (5) | 0.0744 (7) | 0.0443 (5) | −0.0092 (5) | −0.0037 (4) | 0.0023 (5) |
C13 | 0.0529 (7) | 0.1169 (9) | 0.0514 (6) | 0.0031 (7) | −0.0221 (5) | 0.0014 (6) |
C14 | 0.0816 (10) | 0.1050 (10) | 0.1099 (11) | −0.0058 (8) | 0.0401 (8) | 0.0562 (8) |
C15 | 0.1792 (15) | 0.0529 (7) | 0.0838 (9) | −0.0324 (9) | −0.0219 (10) | 0.0061 (6) |
C16 | 0.0592 (8) | 0.0759 (8) | 0.0776 (8) | 0.0120 (6) | 0.0143 (7) | −0.0036 (6) |
C18 | 0.0320 (5) | 0.0500 (5) | 0.0322 (5) | 0.0013 (4) | −0.0057 (4) | 0.0081 (4) |
C19 | 0.0603 (7) | 0.0458 (5) | 0.0364 (5) | −0.0076 (5) | −0.0180 (5) | −0.0013 (5) |
C20 | 0.0642 (7) | 0.0436 (5) | 0.0374 (5) | −0.0019 (5) | −0.0021 (5) | −0.0092 (5) |
C21 | 0.0539 (6) | 0.0551 (6) | 0.0423 (5) | 0.0033 (5) | 0.0119 (5) | 0.0007 (5) |
C22 | 0.0476 (6) | 0.0299 (5) | 0.0391 (5) | 0.0002 (4) | −0.0047 (5) | −0.0016 (4) |
C23 | 0.0554 (7) | 0.0409 (5) | 0.0279 (5) | 0.0142 (5) | −0.0083 (4) | −0.0019 (4) |
C24 | 0.0591 (7) | 0.0740 (7) | 0.0454 (6) | 0.0346 (6) | 0.0024 (5) | 0.0179 (6) |
C25 | 0.1130 (11) | 0.0746 (8) | 0.0633 (8) | 0.0553 (9) | −0.0070 (8) | 0.0163 (7) |
C26 | 0.1703 (14) | 0.0416 (6) | 0.0938 (10) | 0.0388 (8) | 0.0010 (10) | 0.0041 (7) |
C27 | 0.1468 (13) | 0.0348 (6) | 0.0658 (7) | −0.0115 (7) | −0.0225 (8) | 0.0008 (5) |
C28 | 0.0722 (7) | 0.0454 (6) | 0.0532 (6) | −0.0075 (6) | −0.0105 (6) | 0.0111 (5) |
C29 | 0.0568 (7) | 0.0490 (6) | 0.0730 (8) | −0.0081 (5) | −0.0204 (6) | 0.0107 (6) |
C30 | 0.0953 (10) | 0.0659 (8) | 0.0958 (9) | −0.0219 (7) | 0.0050 (8) | 0.0279 (7) |
C31 | 0.0543 (9) | 0.1506 (13) | 0.0780 (9) | 0.0262 (8) | −0.0079 (7) | 0.0356 (8) |
C32 | 0.1277 (13) | 0.1332 (11) | 0.0905 (10) | 0.0972 (10) | 0.0380 (9) | 0.0356 (9) |
C33 | 0.0996 (9) | 0.0641 (7) | 0.0658 (7) | −0.0394 (7) | −0.0031 (7) | −0.0063 (6) |
O17—C1 | 1.4472 (9) | C11—C13 | 1.5055 (12) |
O17—C18 | 1.4507 (9) | C18—C19 | 1.5033 (11) |
C1—C2 | 1.4895 (11) | C18—C23 | 1.5426 (10) |
C1—C6 | 1.5380 (11) | C19—C20 | 1.2999 (12) |
C2—C3 | 1.4756 (12) | C19—C33 | 1.5237 (12) |
C2—C16 | 1.3366 (13) | C20—C21 | 1.4878 (12) |
C3—C4 | 1.5454 (12) | C21—C22 | 1.5130 (12) |
C4—C5 | 1.5273 (11) | C22—C23 | 1.5119 (12) |
C5—C6 | 1.5289 (11) | C22—C28 | 1.5198 (12) |
C5—C11 | 1.5059 (12) | C22—C29 | 1.5100 (13) |
C5—C12 | 1.5170 (11) | C23—C24 | 1.5714 (11) |
C6—C7 | 1.5691 (11) | C24—C25 | 1.539 (2) |
C7—C8 | 1.5237 (14) | C24—C31 | 1.546 (2) |
C7—C14 | 1.531 (2) | C24—C32 | 1.5187 (14) |
C7—C15 | 1.5343 (14) | C25—C26 | 1.554 (2) |
C8—C9 | 1.518 (2) | C26—C27 | 1.542 (2) |
C9—C10 | 1.5139 (15) | C27—C28 | 1.5096 (14) |
C10—C11 | 1.5175 (13) | C28—C29 | 1.5240 (12) |
C11—C12 | 1.5214 (12) | C28—C30 | 1.5354 (14) |
C1—O17—C18 | 115.68 (6) | O17—C18—C19 | 107.13 (7) |
O17—C1—C2 | 110.69 (7) | O17—C18—C23 | 108.54 (6) |
O17—C1—C6 | 104.43 (6) | C19—C18—C23 | 113.57 (7) |
C2—C1—C6 | 113.71 (7) | C18—C19—C20 | 123.15 (8) |
C1—C2—C3 | 115.92 (8) | C18—C19—C33 | 115.29 (8) |
C1—C2—C16 | 120.77 (9) | C20—C19—C33 | 121.36 (8) |
C3—C2—C16 | 123.30 (9) | C19—C20—C21 | 124.96 (8) |
C2—C3—C4 | 110.60 (7) | C20—C21—C22 | 111.17 (7) |
C3—C4—C5 | 109.71 (7) | C21—C22—C23 | 114.21 (7) |
C4—C5—C6 | 113.77 (7) | C21—C22—C28 | 118.78 (8) |
C4—C5—C11 | 121.09 (7) | C21—C22—C29 | 116.54 (8) |
C4—C5—C12 | 116.13 (7) | C23—C22—C28 | 118.83 (7) |
C6—C5—C11 | 118.27 (7) | C23—C22—C29 | 117.71 (7) |
C6—C5—C12 | 116.75 (7) | C28—C22—C29 | 60.40 (6) |
C11—C5—C12 | 60.43 (5) | C18—C23—C22 | 110.43 (7) |
C1—C6—C5 | 110.69 (6) | C18—C23—C24 | 114.90 (8) |
C1—C6—C7 | 115.05 (7) | C22—C23—C24 | 114.30 (7) |
C5—C6—C7 | 114.34 (7) | C23—C24—C25 | 110.65 (9) |
C6—C7—C8 | 111.71 (8) | C23—C24—C31 | 112.64 (8) |
C6—C7—C14 | 114.74 (8) | C23—C24—C32 | 109.47 (8) |
C6—C7—C15 | 107.29 (8) | C25—C24—C31 | 105.88 (9) |
C8—C7—C14 | 107.39 (9) | C25—C24—C32 | 112.36 (9) |
C8—C7—C15 | 107.98 (9) | C31—C24—C32 | 105.74 (11) |
C14—C7—C15 | 107.47 (10) | C24—C25—C26 | 117.91 (10) |
C7—C8—C9 | 120.16 (10) | C25—C26—C27 | 115.54 (8) |
C8—C9—C10 | 114.39 (9) | C26—C27—C28 | 111.71 (10) |
C9—C10—C11 | 113.77 (8) | C22—C28—C27 | 115.83 (9) |
C5—C11—C10 | 115.66 (8) | C22—C28—C29 | 59.48 (6) |
C5—C11—C12 | 60.14 (5) | C22—C28—C30 | 119.74 (8) |
C5—C11—C13 | 120.82 (8) | C27—C28—C29 | 117.30 (8) |
C10—C11—C12 | 117.15 (8) | C27—C28—C30 | 114.76 (8) |
C10—C11—C13 | 113.74 (8) | C29—C28—C30 | 118.75 (10) |
C12—C11—C13 | 119.26 (8) | C22—C29—C28 | 60.12 (6) |
C5—C12—C11 | 59.42 (5) |
Experimental details
Crystal data | |
Chemical formula | C32H50O |
Mr | 450.75 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 298 |
a, b, c (Å) | 8.7475 (2), 15.553 (1), 20.359 (1) |
V (Å3) | 2769.8 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.06 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | KappaCCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3021, 2912, 2673 |
Rint | 0.074 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.086, 0.051, 2.12 |
No. of reflections | 2673 |
No. of parameters | 303 |
No. of restraints | ? |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.28, −0.24 |
Computer programs: KappaCCD Reference Manual(Nonius, 1998), DENZO and SCALEPAK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), maXus (Mackay et al., 1999), ORTEPII (Johnson, 1976), maXus.
La réactivité des himachalènes (l'α, le β - et le γ cis-himachalène), constituants principaux de l'huile essentielle de Cèdre de l'Atlas, a été largement étudiée (Joseph & Dev, 1968; Lassaba et al., 1997, 1998), dans le but d'obtenir des dérivés possédant un pouvoir olfactif utilisable dans l'industrie de la parfumerie. Le résultat que nous rapportons ici concerne l'étude structurale du produit de réarrangement de l'époxyde (1S,3S,8R,9S,10R)-9,10-époxy-3,7,7,10 - tétraméthyltricyclo[6,4,0,01,3]- dodécane 2 obtenu à partir du β- himachalène 1. L'action du dichlorocarbène sur le β-himachalène 1 conduit régiosélectivement et stéréosélectivement avec un rendement de 50% au (1S,3R,8S)-2,2-dichloro-3,7,7,10-tetraméthyltricyclo[6.4.0.01,3]- dodéc-9-ène 2 dont la structure a été établie à partir des données spectrales RMN 1H, 13 C e t R·X. (Auhmani et al., 1999). Cette stéréosélectivité est justifiée par une étude des modèles de Dreiding qui montrent que la face β de la double liaison C6—C7 est fortement protégée par le groupement méthyle en position 11. En présence du sodium dans le méthanol (Bertrand & Maurin, 1967; Sacquet et al., 1971), le produit 2 se transforme quantitativement au (1S,3S,8S)-3,7,7,10-tetraméthyltricyclo[6.4.0.01,3]dodéc-9-ène 3. L'action d'un équivalent d'acide méta-chloroperbenoique (m-CPBA) sur 3 conduit à deux époxydes avec un rendement de 77%. L'obtention de ces deux produits s'explique par l'accessibilité des faces α et β de la double liaison C2—C3 du β-himachalène. Lors de la chromatographie du mélange réactionnel de ces deux époxydes sur une colonne de gel de silice, nous avons obtenu un seul époxyde et un produit de réarrangement que nous n'avons pas pu identifier en se basant seulement sur les données spectrales de RMN 1H et 13 C. Une étude cristalline au RX d'un monocristal de ce produit a permis de l'identifier au (1S,3S,8R,9S)-3,7,7,10-tetraméthyl-9-((1S,3S,8R,9S)-3,7,7-triméthyl-10 - méthylène-tricyclo[6.4.0.01,3]dodéc-9-yloxy)-tricyclo[6.4.0.01,3]- dodéc-10-éne et de déduire d'une part que sa formation est due au réarrangement de l'époxyde (1S,3S,8R,9S,10R)-9,10-époxy-3,7,7,10 - tétraméthyltricyclo[6,4,0,01,3]- dodécane et d'attribuer d'autre part la structure (1S,3S,8R,9R,10S)-9,10-époxy-3,7,7,10 - tétraméthyltricyclo[6,4,0,01,3]- dodécane à l'époxyde isolé.