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In the molecule of the title compound, C
13H
18O
3, there is a
syn relationship between the two vicinal methyl groups. The six-membered ring adopts a chair conformation, with one equatorial and two axial groups, and the furyl group is almost parallel to the ketone group. Intermolecular hydrogen bonds [O—H
O=C 2.814 (3) Å] form chains along [100].
Supporting information
CCDC reference: 188618
A solution of 2-methyl-2-cyclohexenone (15 mmol) in anhydrous ether (15 ml) was
added dropwise to a stirred solution of lithium dimethylcuprate (30 mmol) in
anhydrous ether (200 ml) at 268 K under a nitrogen atmosphere. A yellow
precipitate was obtained, and after stirring for 30 min, a 1 M ethereal
solution of zinc chloride (30 ml) was added, followed by a solution of
furan-3-carbaldehyde (18.75 mmol) in anhydrous ether (15 ml). Stirring was
continued for 15 min at 268 K, and the reaction mixture was poured into 20%
aqueous ammonium chloride (350 ml). After separation, the aqueous phase was
extracted with ether (2 × 30 ml). The combined ethereal phases were
washed with 10% aqueous ammonium chloride (2 × 30 ml), brine (2 ×
30 ml), dried and concentrated. The crude product was separated by column
chromatography, yielding two compounds. The most polar product [(IIa) in 28%
yield] was obtained as colorless prisms (m.p. 360–361 K) after purification
and recrystallization from ether–hexane. The epimeric stereochemical
relationship between (IIa) and (IIb) was established by oxidation (Jones) of
each diastereoisomer to the same β-diketone.
The positional parameters of the hydroxy H atom were refined, while those of the
other H atoms were calculated geometrically (C—H = 0.93–0.98 Å). All H
atoms were fixed with Uiso = 1.2Uew of the attached non-H atom. The
absolute configuration could not be determined.
Data collection: SMART (Bruker, 2000); cell refinement: SMART (Bruker, 2000); data reduction: SAINT-Plus (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
2-[(3-Furyl)(hydroxy)methyl]-2,3-dimethylcyclohexanone
top
Crystal data top
C13H18O3 | Dx = 1.187 Mg m−3 |
Mr = 222.27 | Melting point = 360–361 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 512 reflections |
a = 7.962 (3) Å | θ = 2.7–29.1° |
b = 8.249 (4) Å | µ = 0.08 mm−1 |
c = 18.931 (9) Å | T = 293 K |
V = 1243.3 (10) Å3 | Prism, colorless |
Z = 4 | 0.24 × 0.20 × 0.14 mm |
F(000) = 480 | |
Data collection top
Bruker CCD area-detector diffractometer | 1045 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.149 |
Graphite monochromator | θmax = 27.5°, θmin = 2.2° |
ϕ and ω scans | h = −10→10 |
11179 measured reflections | k = −10→10 |
1667 independent reflections | l = −24→24 |
Refinement top
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | w = 1/[σ2(Fo2) + (0.0271P)2] where P = (Fo2 + 2Fc2)/3 |
1667 reflections | (Δ/σ)max = 0.021 |
149 parameters | Δρmax = 0.15 e Å−3 |
0 restraints | Δρmin = −0.12 e Å−3 |
Crystal data top
C13H18O3 | V = 1243.3 (10) Å3 |
Mr = 222.27 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.962 (3) Å | µ = 0.08 mm−1 |
b = 8.249 (4) Å | T = 293 K |
c = 18.931 (9) Å | 0.24 × 0.20 × 0.14 mm |
Data collection top
Bruker CCD area-detector diffractometer | 1045 reflections with I > 2σ(I) |
11179 measured reflections | Rint = 0.149 |
1667 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.99 | Δρmax = 0.15 e Å−3 |
1667 reflections | Δρmin = −0.12 e Å−3 |
149 parameters | |
Special details top
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. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | −0.0547 (2) | 0.7757 (3) | 0.10759 (12) | 0.0733 (7) | |
O2 | 0.2303 (3) | 0.6215 (3) | 0.00156 (11) | 0.0610 (6) | |
H2 | 0.287 (4) | 0.644 (3) | −0.0319 (15) | 0.061 (11)* | |
C1 | 0.0978 (4) | 0.7891 (3) | 0.11498 (16) | 0.0543 (7) | |
C2 | 0.2099 (3) | 0.6414 (3) | 0.12763 (14) | 0.0496 (7) | |
C3 | 0.3079 (4) | 0.6697 (4) | 0.19776 (16) | 0.0627 (8) | |
H3 | 0.3942 | 0.5852 | 0.2008 | 0.075* | |
C4 | 0.3997 (4) | 0.8345 (4) | 0.1983 (2) | 0.0823 (11) | |
H4A | 0.4549 | 0.8490 | 0.2435 | 0.099* | |
H4B | 0.4855 | 0.8345 | 0.1619 | 0.099* | |
C5 | 0.2803 (5) | 0.9755 (4) | 0.1856 (2) | 0.0874 (12) | |
H5A | 0.3439 | 1.0756 | 0.1829 | 0.105* | |
H5B | 0.2028 | 0.9841 | 0.2250 | 0.105* | |
C6 | 0.1809 (4) | 0.9516 (3) | 0.1167 (2) | 0.0716 (10) | |
H6A | 0.0963 | 1.0357 | 0.1127 | 0.086* | |
H6B | 0.2564 | 0.9616 | 0.0767 | 0.086* | |
C7 | 0.3326 (3) | 0.6299 (3) | 0.06395 (15) | 0.0511 (7) | |
H7 | 0.3971 | 0.7309 | 0.0620 | 0.061* | |
C8 | 0.1032 (3) | 0.4871 (3) | 0.13147 (19) | 0.0644 (9) | |
H8A | 0.0682 | 0.4568 | 0.0848 | 0.077* | |
H8B | 0.0060 | 0.5068 | 0.1603 | 0.077* | |
H8C | 0.1684 | 0.4010 | 0.1518 | 0.077* | |
C9 | 0.1950 (4) | 0.6520 (4) | 0.26324 (16) | 0.0965 (12) | |
H9A | 0.2521 | 0.6949 | 0.3038 | 0.116* | |
H9B | 0.1701 | 0.5395 | 0.2709 | 0.116* | |
H9C | 0.0923 | 0.7107 | 0.2559 | 0.116* | |
O10 | 0.6957 (2) | 0.3527 (3) | 0.07977 (12) | 0.0755 (7) | |
C11 | 0.6202 (3) | 0.5009 (4) | 0.08266 (17) | 0.0624 (8) | |
H11 | 0.6759 | 0.5968 | 0.0936 | 0.075* | |
C12 | 0.4551 (3) | 0.4917 (3) | 0.06766 (15) | 0.0504 (7) | |
C13 | 0.4257 (4) | 0.3236 (3) | 0.05373 (18) | 0.0645 (8) | |
H13 | 0.3237 | 0.2765 | 0.0414 | 0.077* | |
C14 | 0.5724 (4) | 0.2472 (4) | 0.06168 (18) | 0.0691 (9) | |
H14 | 0.5878 | 0.1364 | 0.0556 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0525 (12) | 0.0876 (15) | 0.0797 (15) | 0.0032 (11) | −0.0070 (12) | 0.0100 (12) |
O2 | 0.0610 (14) | 0.0709 (14) | 0.0509 (12) | −0.0047 (11) | −0.0005 (13) | 0.0113 (11) |
C1 | 0.0532 (17) | 0.0607 (19) | 0.0491 (18) | 0.0001 (14) | −0.0011 (16) | 0.0009 (14) |
C2 | 0.0513 (16) | 0.0477 (16) | 0.0496 (16) | −0.0043 (13) | −0.0005 (15) | 0.0009 (13) |
C3 | 0.066 (2) | 0.0674 (19) | 0.0550 (18) | 0.0067 (16) | −0.0111 (17) | −0.0015 (16) |
C4 | 0.079 (2) | 0.085 (2) | 0.084 (2) | −0.006 (2) | −0.021 (2) | −0.025 (2) |
C5 | 0.096 (3) | 0.061 (2) | 0.105 (3) | −0.009 (2) | 0.001 (3) | −0.020 (2) |
C6 | 0.075 (2) | 0.0487 (19) | 0.091 (3) | 0.0036 (15) | −0.002 (2) | 0.0025 (17) |
C7 | 0.0528 (16) | 0.0461 (15) | 0.0543 (17) | −0.0121 (13) | −0.0063 (15) | 0.0041 (15) |
C8 | 0.0647 (19) | 0.0604 (18) | 0.068 (2) | −0.0102 (16) | 0.0073 (17) | 0.0102 (17) |
C9 | 0.127 (3) | 0.110 (3) | 0.053 (2) | −0.005 (3) | −0.006 (2) | −0.002 (2) |
O10 | 0.0615 (13) | 0.0736 (15) | 0.0915 (17) | 0.0112 (12) | 0.0043 (13) | 0.0010 (13) |
C11 | 0.0557 (17) | 0.0525 (17) | 0.079 (2) | −0.0034 (16) | 0.0073 (17) | 0.0020 (17) |
C12 | 0.0513 (16) | 0.0490 (15) | 0.0508 (16) | −0.0049 (15) | 0.0024 (16) | −0.0032 (15) |
C13 | 0.0597 (19) | 0.0564 (17) | 0.077 (2) | −0.0062 (15) | −0.0081 (18) | −0.0052 (17) |
C14 | 0.083 (2) | 0.0523 (16) | 0.072 (2) | 0.0048 (19) | 0.007 (2) | −0.0026 (17) |
Geometric parameters (Å, º) top
O1—C1 | 1.227 (3) | C6—H6B | 0.9700 |
O2—C7 | 1.436 (3) | C7—C12 | 1.502 (4) |
O2—H2 | 0.80 (3) | C7—H7 | 0.9800 |
C1—C6 | 1.496 (4) | C8—H8A | 0.9600 |
C1—C2 | 1.529 (4) | C8—H8B | 0.9600 |
C2—C8 | 1.532 (3) | C8—H8C | 0.9600 |
C2—C7 | 1.554 (4) | C9—H9A | 0.9600 |
C2—C3 | 1.558 (4) | C9—H9B | 0.9600 |
C3—C9 | 1.538 (4) | C9—H9C | 0.9600 |
C3—C4 | 1.544 (4) | O10—C14 | 1.356 (3) |
C3—H3 | 0.9800 | O10—C11 | 1.364 (3) |
C4—C5 | 1.521 (4) | C11—C12 | 1.347 (3) |
C4—H4A | 0.9700 | C11—H11 | 0.9300 |
C4—H4B | 0.9700 | C12—C13 | 1.430 (4) |
C5—C6 | 1.538 (5) | C13—C14 | 1.335 (4) |
C5—H5A | 0.9700 | C13—H13 | 0.9300 |
C5—H5B | 0.9700 | C14—H14 | 0.9300 |
C6—H6A | 0.9700 | | |
| | | |
C7—O2—H2 | 109 (2) | H6A—C6—H6B | 108.0 |
O1—C1—C6 | 121.4 (3) | O2—C7—C12 | 111.7 (2) |
O1—C1—C2 | 121.6 (3) | O2—C7—C2 | 106.5 (2) |
C6—C1—C2 | 116.9 (2) | C12—C7—C2 | 114.7 (2) |
C1—C2—C8 | 110.2 (2) | O2—C7—H7 | 107.9 |
C1—C2—C7 | 107.1 (2) | C12—C7—H7 | 107.9 |
C8—C2—C7 | 109.5 (2) | C2—C7—H7 | 107.9 |
C1—C2—C3 | 107.9 (2) | C2—C8—H8A | 109.5 |
C8—C2—C3 | 111.2 (2) | C2—C8—H8B | 109.5 |
C7—C2—C3 | 110.8 (2) | H8A—C8—H8B | 109.5 |
C9—C3—C4 | 110.8 (3) | C2—C8—H8C | 109.5 |
C9—C3—C2 | 112.3 (2) | H8A—C8—H8C | 109.5 |
C4—C3—C2 | 112.0 (3) | H8B—C8—H8C | 109.5 |
C9—C3—H3 | 107.1 | C3—C9—H9A | 109.5 |
C4—C3—H3 | 107.1 | C3—C9—H9B | 109.5 |
C2—C3—H3 | 107.1 | H9A—C9—H9B | 109.5 |
C5—C4—C3 | 112.1 (2) | C3—C9—H9C | 109.5 |
C5—C4—H4A | 109.2 | H9A—C9—H9C | 109.5 |
C3—C4—H4A | 109.2 | H9B—C9—H9C | 109.5 |
C5—C4—H4B | 109.2 | C14—O10—C11 | 105.4 (2) |
C3—C4—H4B | 109.2 | C12—C11—O10 | 111.8 (3) |
H4A—C4—H4B | 107.9 | C12—C11—H11 | 124.1 |
C4—C5—C6 | 110.9 (3) | O10—C11—H11 | 124.1 |
C4—C5—H5A | 109.4 | C11—C12—C13 | 104.7 (3) |
C6—C5—H5A | 109.5 | C11—C12—C7 | 126.9 (2) |
C4—C5—H5B | 109.5 | C13—C12—C7 | 128.4 (2) |
C6—C5—H5B | 109.4 | C14—C13—C12 | 107.1 (3) |
H5A—C5—H5B | 108.0 | C14—C13—H13 | 126.5 |
C1—C6—C5 | 111.2 (3) | C12—C13—H13 | 126.5 |
C1—C6—H6A | 109.4 | C13—C14—O10 | 111.1 (3) |
C5—C6—H6A | 109.4 | C13—C14—H14 | 124.5 |
C1—C6—H6B | 109.4 | O10—C14—H14 | 124.5 |
C5—C6—H6B | 109.4 | | |
| | | |
O1—C1—C2—C8 | −1.8 (4) | C1—C2—C7—O2 | −56.5 (3) |
C6—C1—C2—C8 | 174.3 (3) | C8—C2—C7—O2 | 63.0 (3) |
O1—C1—C2—C7 | 117.3 (3) | C3—C2—C7—O2 | −173.9 (2) |
C6—C1—C2—C7 | −66.6 (3) | C1—C2—C7—C12 | 179.3 (2) |
O1—C1—C2—C3 | −123.4 (3) | C8—C2—C7—C12 | −61.2 (3) |
C6—C1—C2—C3 | 52.8 (3) | C3—C2—C7—C12 | 61.9 (3) |
C1—C2—C3—C9 | 73.1 (3) | C14—O10—C11—C12 | 0.5 (3) |
C8—C2—C3—C9 | −47.9 (3) | O10—C11—C12—C13 | −0.5 (4) |
C7—C2—C3—C9 | −170.0 (3) | O10—C11—C12—C7 | −178.4 (3) |
C1—C2—C3—C4 | −52.3 (3) | O2—C7—C12—C11 | 133.0 (3) |
C8—C2—C3—C4 | −173.3 (2) | C2—C7—C12—C11 | −105.6 (3) |
C7—C2—C3—C4 | 64.6 (3) | O2—C7—C12—C13 | −44.4 (4) |
C9—C3—C4—C5 | −69.8 (4) | C2—C7—C12—C13 | 77.0 (4) |
C2—C3—C4—C5 | 56.5 (4) | C11—C12—C13—C14 | 0.3 (4) |
C3—C4—C5—C6 | −55.0 (4) | C7—C12—C13—C14 | 178.2 (3) |
O1—C1—C6—C5 | 122.6 (3) | C12—C13—C14—O10 | 0.0 (4) |
C2—C1—C6—C5 | −53.5 (4) | C11—O10—C14—C13 | −0.3 (4) |
C4—C5—C6—C1 | 52.1 (4) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.80 (3) | 2.02 (3) | 2.814 (3) | 172 (3) |
Symmetry code: (i) x+1/2, −y+3/2, −z. |
Experimental details
Crystal data |
Chemical formula | C13H18O3 |
Mr | 222.27 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.962 (3), 8.249 (4), 18.931 (9) |
V (Å3) | 1243.3 (10) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.24 × 0.20 × 0.14 |
|
Data collection |
Diffractometer | Bruker CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11179, 1667, 1045 |
Rint | 0.149 |
(sin θ/λ)max (Å−1) | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.098, 0.99 |
No. of reflections | 1667 |
No. of parameters | 149 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.15, −0.12 |
Selected geometric parameters (Å, º) topO1—C1 | 1.227 (3) | O10—C14 | 1.356 (3) |
O2—C7 | 1.436 (3) | O10—C11 | 1.364 (3) |
C1—C2 | 1.529 (4) | C11—C12 | 1.347 (3) |
C2—C8 | 1.532 (3) | C12—C13 | 1.430 (4) |
C2—C7 | 1.554 (4) | C13—C14 | 1.335 (4) |
C2—C3 | 1.558 (4) | | |
| | | |
O1—C1—C6 | 121.4 (3) | C14—O10—C11 | 105.4 (2) |
O1—C1—C2 | 121.6 (3) | C12—C11—O10 | 111.8 (3) |
C6—C1—C2 | 116.9 (2) | C11—C12—C13 | 104.7 (3) |
C1—C2—C8 | 110.2 (2) | C14—C13—C12 | 107.1 (3) |
C1—C2—C7 | 107.1 (2) | C13—C14—O10 | 111.1 (3) |
O2—C7—C2 | 106.5 (2) | | |
| | | |
O1—C1—C2—C8 | −1.8 (4) | C1—C2—C7—O2 | −56.5 (3) |
O1—C1—C2—C7 | 117.3 (3) | C8—C2—C7—O2 | 63.0 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O1i | 0.80 (3) | 2.02 (3) | 2.814 (3) | 172 (3) |
Symmetry code: (i) x+1/2, −y+3/2, −z. |
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Many sesquiterpenes possessing a furan ring have been isolated from plant species and among them, the furanoeremophilanes, (I), are the most abundant (Hikino & Konno, 1976; Kuroyanagi et al., 1985; Torres et al., 1999). The interesting linearly fused furo[2,3-b]decalin framework containing syn-vicinal dimethyl groups at atoms C-4a and C-5 of these compounds, together with the biological activities shown by some of them, have attracted the attention of many synthetic chemists (Irie et al., 1982; Jacobi et al., 1984; Koike et al., 1999; Miyashita et al., 1980; Tada et al., 1980; Yamakawa et al., 1983). We have designed a synthetic strategy for the basic skeleton (I), in which the key step is the preparation of compounds such as ketol (II). Since NMR analyses of (IIa) and (IIb) did not allow conclusive assignment of the relative stereochemistry of the methyl groups, we carried out the X-ray analysis of (IIa) which unequivocally established this relationship as syn.
Fig. 1 shows the molecular structure of (IIa), and selected bond distances, angles and torsion angles are listed in Table 1. The cyclohexanone ring adopts a chair conformation with the C3-methyl and the C2-hydroxymethyl groups in anti-diaxial orientations. This is an unexpected and unusual result since, in principle, the anti-diequatorial conformer, (IIa') (obtained by flipping the cyclohexanone ring), should be more stable.
The carbonyl and methyl (C8) groups on C2 are almost coplanar, with a O1—C1—C2—C8 torsion angle of -1.8 (4)° and the mean deviation from the plane of the four atoms being 0.007 Å, and the hydroxy moiety C2—-C7—O2 is almost perpendicular [86.84 (14)°] to this four-atom plane. This geometry does not allow intramolecular hydrogen bonding between the hydroxy and ketone groups. The fragment C1(═O1)—C2—C6 of the cyclohexanone ring is practically planar, within experimental error [the maximum deviation from the plane is -0.020 (3) for atom C1] and the C1\dn O1 bond distance [1.227 (3) Å] is within the normal range. Similar results are found in previously reported cyclohexanones (Barluenga et al., 1993; Brunner & Maas, 1995; Hernández-Ortega et al., 2001; Rowland et al., 1998).
The furyl group is essentially planar, within experimental error (the mean deviation from the plane is 0.0018 Å). This group is almost parallel to the ketone group [12.82 (9)°] and is inclined at an angle of 47.23 (17)° with respect to the best plane described by atoms C2, C3, C5 and C6 of the cyclohexanone ring (the mean deviation from this pane is 0.0051 Å).
The molecules are stacked in the crystal along the a axis, with the cyclohexanone and furyl groups almost perpendicular to the ac plane (Fig. 2). The molecules are linked by intermolecular hydrogen bonds between the hydroxy and ring carbonyl groups (Table 2). The preference for intermolecular as opposed to intramolecular hydrogen bonding is due to the orientation of the (3-furyl)(hydroxy)methyl group on the cyclohexanone ring.