Literature DB >> 23795020

(1S,3R,8R)-2,2-Di-chloro-3,7,7,10-tetra-methyl-tri-cyclo-[6.4.0.0(1,3)]dodec-9-en-11-one.

Naja Ourhriss¹, Ahmed Benharref, Abdelouahd Oukhrib, Jean-Claude Daran, Moha Berraho.

Abstract

The title compound, C16H22Cl2O, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings and an additional three-membered ring arising from the reaction of himachalene with di-chloro-carbene. The six-membered ring has an envelope conformation, with the C atom belonging to the three-membered ring forming the flap, whereas the seven-membered ring displays a screw-boat conformation; the dihedral angle between the rings (all atoms) is 59.65 (14)°.

Entities: Chemical Disease Species

Year: 2013 PMID： 23795020 PMCID： PMC3684918 DOI： 10.1107/S1600536813011781

Source DB: PubMed Journal: Acta Crystallogr Sect E Struct Rep Online ISSN： 1600-5368

Related literature

For background to the essential oil of the Alas cedar (Cedrus atlantica), see: Joseph & Dev (1968 ▶); Plattier & Teiseire (1974 ▶). For the reactivity and biological properties of β-himachalene, see: Benharref et al. (2012 ▶); Chekroun et al. (2000 ▶); El Jamili et al. (2002 ▶); Lassaba et al. (1998 ▶); Dakir et al. (2004 ▶); Daoubi et al. (2004 ▶). For conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H22Cl2O M = 301.24 Monoclinic, a = 8.8780 (3) Å b = 10.3340 (3) Å c = 8.9230 (3) Å β = 108.805 (4)° V = 774.94 (4) Å3 Z = 2 Cu Kα radiation μ = 3.67 mm−1 T = 180 K 0.30 × 0.25 × 0.21 mm

Data collection

Agilent Xcalibur (Eos, Gemini ultra) diffractometer Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T min = 0.761, T max = 1.000 2787 measured reflections 1835 independent reflections 1779 reflections with I > 2σ(I) R int = 0.027 θmax = 60.6°

Refinement

R[F 2 > 2σ(F 2)] = 0.028 wR(F 2) = 0.065 S = 1.03 1835 reflections 176 parameters 1 restraint H-atom parameters constrained Δρmax = 0.16 e Å−3 Δρmin = −0.17 e Å−3 Absolute structure: Flack & Bernardinelli (2000 ▶), 614 Friedel pairs Flack parameter: 0.014 (15) Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶). Click here for additional data file. Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813011781/tk5222sup1.cif Click here for additional data file. Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813011781/tk5222Isup2.hkl Click here for additional data file. Supplementary material file. DOI: 10.1107/S1600536813011781/tk5222Isup3.cml Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C₁₆H₂₂Cl₂O	F(000) = 320
M_r = 301.24	D_x = 1.291 Mg m⁻³
Monoclinic, P2₁	Cu Kα radiation, λ = 1.5418 Å
Hall symbol: P 2yb	Cell parameters from 1955 reflections
a = 8.8780 (3) Å	θ = 4.3–60.5°
b = 10.3340 (3) Å	µ = 3.67 mm⁻¹
c = 8.9230 (3) Å	T = 180 K
β = 108.805 (4)°	Block, colourless
V = 774.94 (4) Å³	0.30 × 0.25 × 0.21 mm
Z = 2

Agilent Xcalibur (Eos, Gemini ultra) diffractometer	1835 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1779 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 16.1978 pixels mm^-1	θ_max = 60.6°, θ_min = 5.2°
ω scans	h = −9→8
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010)	k = −11→11
T_min = 0.761, T_max = 1.000	l = −8→10
2787 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)] = 0.028	H-atom parameters constrained
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.0268P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1835 reflections	Δρ_max = 0.16 e Å⁻³
176 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint	Absolute structure: Flack & Bernardinelli (2000), 614 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.014 (15)

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 > 2σ(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	U_iso*/U_eq
Cl1	0.37702 (8)	0.87301 (6)	0.63481 (9)	0.04024 (19)
Cl2	0.53172 (8)	0.67535 (7)	0.51438 (9)	0.0422 (2)
O1	0.7317 (2)	0.4592 (2)	0.9131 (3)	0.0472 (6)
C1	0.3527 (3)	0.6081 (2)	0.7144 (3)	0.0230 (6)
C2	0.3817 (3)	0.7052 (2)	0.6004 (3)	0.0278 (6)
C3	0.2321 (3)	0.6249 (2)	0.5493 (3)	0.0280 (6)
C4	0.0763 (3)	0.6914 (3)	0.5429 (3)	0.0367 (7)
H4A	0.0196	0.7190	0.4329	0.044*
H4B	0.1000	0.7696	0.6105	0.044*
C5	−0.0311 (3)	0.6006 (3)	0.5995 (4)	0.0417 (8)
H5A	−0.1098	0.6536	0.6294	0.050*
H5B	−0.0906	0.5446	0.5100	0.050*
C6	0.0567 (3)	0.5144 (3)	0.7398 (3)	0.0366 (7)
H6A	0.1202	0.4510	0.7025	0.044*
H6B	−0.0241	0.4650	0.7708	0.044*
C7	0.1685 (3)	0.5800 (3)	0.8897 (3)	0.0310 (6)
C8	0.3075 (3)	0.6569 (3)	0.8553 (3)	0.0249 (6)
H8	0.2677	0.7473	0.8285	0.030*
C9	0.4529 (3)	0.6672 (3)	0.9982 (3)	0.0276 (6)
H9	0.4453	0.7195	1.0830	0.033*
C10	0.5923 (3)	0.6092 (3)	1.0171 (3)	0.0289 (7)
C11	0.6079 (3)	0.5170 (3)	0.8973 (3)	0.0289 (6)
C12	0.4618 (3)	0.4911 (2)	0.7555 (3)	0.0276 (6)
H12A	0.4028	0.4166	0.7788	0.033*
H12B	0.4953	0.4681	0.6633	0.033*
C13	0.2113 (4)	0.5220 (3)	0.4243 (3)	0.0410 (7)
H13A	0.1623	0.5602	0.3193	0.061*
H13B	0.1426	0.4530	0.4411	0.061*
H13C	0.3154	0.4858	0.4313	0.061*
C14	0.0742 (4)	0.6748 (4)	0.9559 (4)	0.0483 (8)
H14A	0.0328	0.7447	0.8794	0.072*
H14B	0.1439	0.7114	1.0555	0.072*
H14C	−0.0145	0.6294	0.9753	0.072*
C15	0.2324 (4)	0.4722 (3)	1.0132 (3)	0.0422 (8)
H15A	0.3011	0.5103	1.1123	0.063*
H15B	0.2937	0.4101	0.9733	0.063*
H15C	0.1429	0.4277	1.0326	0.063*
C16	0.7361 (3)	0.6288 (3)	1.1612 (4)	0.0395 (8)
H16A	0.8121	0.6856	1.1345	0.059*
H16B	0.7863	0.5450	1.1974	0.059*
H16C	0.7034	0.6686	1.2456	0.059*

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0401 (4)	0.0234 (3)	0.0606 (5)	0.0026 (3)	0.0209 (3)	0.0072 (3)
Cl2	0.0418 (4)	0.0447 (4)	0.0518 (4)	0.0023 (3)	0.0313 (3)	0.0049 (4)
O1	0.0303 (11)	0.0442 (12)	0.0622 (14)	0.0111 (10)	0.0081 (9)	0.0002 (11)
C1	0.0221 (13)	0.0210 (12)	0.0259 (15)	0.0004 (10)	0.0077 (10)	−0.0016 (11)
C2	0.0249 (14)	0.0268 (14)	0.0358 (16)	0.0033 (10)	0.0153 (11)	0.0027 (12)
C3	0.0240 (14)	0.0314 (15)	0.0292 (15)	0.0012 (11)	0.0093 (11)	0.0024 (11)
C4	0.0246 (15)	0.0439 (17)	0.0376 (17)	0.0060 (12)	0.0046 (11)	0.0013 (14)
C5	0.0207 (14)	0.0578 (19)	0.0425 (18)	−0.0052 (13)	0.0044 (12)	−0.0043 (16)
C6	0.0323 (16)	0.0418 (16)	0.0368 (17)	−0.0130 (13)	0.0126 (12)	−0.0085 (13)
C7	0.0290 (15)	0.0355 (15)	0.0319 (16)	−0.0079 (12)	0.0146 (11)	−0.0076 (13)
C8	0.0224 (13)	0.0252 (14)	0.0273 (14)	0.0002 (11)	0.0084 (10)	−0.0021 (13)
C9	0.0299 (15)	0.0271 (13)	0.0277 (14)	−0.0078 (12)	0.0119 (10)	−0.0036 (13)
C10	0.0274 (16)	0.0276 (14)	0.0301 (16)	−0.0066 (12)	0.0073 (11)	0.0058 (12)
C11	0.0249 (15)	0.0258 (13)	0.0362 (16)	0.0015 (11)	0.0100 (11)	0.0087 (12)
C12	0.0279 (14)	0.0232 (13)	0.0333 (15)	0.0039 (11)	0.0121 (11)	−0.0018 (12)
C13	0.0425 (17)	0.0523 (18)	0.0275 (16)	−0.0021 (14)	0.0105 (13)	−0.0078 (14)
C14	0.0409 (17)	0.0547 (19)	0.061 (2)	−0.0082 (16)	0.0327 (15)	−0.0181 (18)
C15	0.0506 (19)	0.0452 (18)	0.0344 (17)	−0.0140 (15)	0.0189 (13)	0.0004 (15)
C16	0.0299 (16)	0.0473 (19)	0.0361 (17)	−0.0025 (12)	0.0033 (12)	0.0105 (14)

Cl1—C2	1.764 (3)	C8—C9	1.497 (3)
Cl2—C2	1.766 (3)	C8—H8	1.0000
O1—C11	1.218 (3)	C9—C10	1.336 (4)
C1—C2	1.509 (4)	C9—H9	0.9500
C1—C12	1.519 (3)	C10—C11	1.472 (4)
C1—C8	1.523 (4)	C10—C16	1.505 (4)
C1—C3	1.526 (3)	C11—C12	1.516 (4)
C2—C3	1.506 (4)	C12—H12A	0.9900
C3—C13	1.509 (4)	C12—H12B	0.9900
C3—C4	1.529 (4)	C13—H13A	0.9800
C4—C5	1.534 (4)	C13—H13B	0.9800
C4—H4A	0.9900	C13—H13C	0.9800
C4—H4B	0.9900	C14—H14A	0.9800
C5—C6	1.529 (4)	C14—H14B	0.9800
C5—H5A	0.9900	C14—H14C	0.9800
C5—H5B	0.9900	C15—H15A	0.9800
C6—C7	1.543 (4)	C15—H15B	0.9800
C6—H6A	0.9900	C15—H15C	0.9800
C6—H6B	0.9900	C16—H16A	0.9800
C7—C14	1.526 (4)	C16—H16B	0.9800
C7—C15	1.541 (4)	C16—H16C	0.9800
C7—C8	1.579 (4)

C2—C1—C12	117.2 (2)	C1—C8—C7	115.1 (2)
C2—C1—C8	119.0 (2)	C9—C8—H8	106.2
C12—C1—C8	112.4 (2)	C1—C8—H8	106.2
C2—C1—C3	59.49 (16)	C7—C8—H8	106.2
C12—C1—C3	121.2 (2)	C10—C9—C8	125.8 (2)
C8—C1—C3	118.0 (2)	C10—C9—H9	117.1
C3—C2—C1	60.82 (17)	C8—C9—H9	117.1
C3—C2—Cl1	121.74 (18)	C9—C10—C11	119.9 (2)
C1—C2—Cl1	121.15 (19)	C9—C10—C16	122.9 (3)
C3—C2—Cl2	119.2 (2)	C11—C10—C16	117.1 (2)
C1—C2—Cl2	119.59 (18)	O1—C11—C10	121.7 (2)
Cl1—C2—Cl2	108.11 (14)	O1—C11—C12	120.5 (2)
C2—C3—C13	119.9 (2)	C10—C11—C12	117.7 (2)
C2—C3—C1	59.68 (17)	C11—C12—C1	111.6 (2)
C13—C3—C1	120.9 (2)	C11—C12—H12A	109.3
C2—C3—C4	117.6 (2)	C1—C12—H12A	109.3
C13—C3—C4	113.3 (2)	C11—C12—H12B	109.3
C1—C3—C4	115.6 (2)	C1—C12—H12B	109.3
C3—C4—C5	111.3 (2)	H12A—C12—H12B	108.0
C3—C4—H4A	109.4	C3—C13—H13A	109.5
C5—C4—H4A	109.4	C3—C13—H13B	109.5
C3—C4—H4B	109.4	H13A—C13—H13B	109.5
C5—C4—H4B	109.4	C3—C13—H13C	109.5
H4A—C4—H4B	108.0	H13A—C13—H13C	109.5
C6—C5—C4	114.8 (2)	H13B—C13—H13C	109.5
C6—C5—H5A	108.6	C7—C14—H14A	109.5
C4—C5—H5A	108.6	C7—C14—H14B	109.5
C6—C5—H5B	108.6	H14A—C14—H14B	109.5
C4—C5—H5B	108.6	C7—C14—H14C	109.5
H5A—C5—H5B	107.6	H14A—C14—H14C	109.5
C5—C6—C7	118.0 (3)	H14B—C14—H14C	109.5
C5—C6—H6A	107.8	C7—C15—H15A	109.5
C7—C6—H6A	107.8	C7—C15—H15B	109.5
C5—C6—H6B	107.8	H15A—C15—H15B	109.5
C7—C6—H6B	107.8	C7—C15—H15C	109.5
H6A—C6—H6B	107.1	H15A—C15—H15C	109.5
C14—C7—C15	108.0 (2)	H15B—C15—H15C	109.5
C14—C7—C6	109.7 (2)	C10—C16—H16A	109.5
C15—C7—C6	106.7 (2)	C10—C16—H16B	109.5
C14—C7—C8	108.2 (2)	H16A—C16—H16B	109.5
C15—C7—C8	111.9 (2)	C10—C16—H16C	109.5
C6—C7—C8	112.2 (2)	H16A—C16—H16C	109.5
C9—C8—C1	110.0 (2)	H16B—C16—H16C	109.5
C9—C8—C7	112.5 (2)

5 in total

1. Regio- and stereoselectivity of beta-himachalene epoxidation by m-CPBA. A theoretical study.

Authors: A Chekroun; A Jarid; A Benharref; A Boutalib
Journal: J Org Chem Date: 2000-07-14 Impact factor: 4.354

2. Screening study for potential lead compounds for natural product-based fungicides: I. Synthesis and in vitro evaluation of coumarins against Botrytis cinerea.

Authors: Mourad Daoubi; Rosa Durán-Patrón; Mohamed Hmamouchi; Rosario Hernández-Galán; Ahmed Benharref; Isidro G Collado
Journal: Pest Manag Sci Date: 2004-09 Impact factor: 4.845