Download citation
Download citation
link to html
The title compound, C22H28O6S, was prepared as a key inter­mediate in the synthesis of coenzyme Q10 via a Friedel–Crafts reaction. The C=C double bond is trans configured. The crystal packing is stabilized by C—H...O contacts.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807043309/bt2497sup1.cif
Contains datablocks 1, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807043309/bt2497IIIsup2.hkl
Contains datablock III

CCDC reference: 663721

Key indicators

  • Single-crystal X-ray study
  • T = 184 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.051
  • wR factor = 0.138
  • Data-to-parameter ratio = 19.0

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.76 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.12 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C8
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

Coenzyme Q10 plays an essential role in the electron-transfer processes necessary for respiration, and is applied as a drug against many diseases. The title compound is the key intermediate to synthesize coenzyme Q10 via a coupling reactions with solanesyl bromide, and it was prepared by coupling tetramethoxytoluene (I) with 4-chioro-2-methyl-1-phenylsulfonyl- 2-butene (II) via Friedel-Crafts reaction.

The crystal packing of the title compound is stabilized by C—H···O contacts.

Related literature top

Do you wish to cite any related literature?

Experimental top

2,3,4,5-Tetramethoxytoluene (I) (10 mmol, 1.0 equiv.), and 4-chioro-2- methyl-1-phenylsulfonyl-2-butene (II) (10 mmol, 1.0 equiv.) were stirred in nitromethane (25 ml), then anhydrous zinc chloride (20 mmol) was added and stirred at room temperature for 8 hrs. Water (50 ml) was added to the reaction mixture and stirred for 10 min. The organic layer was separated, dried with anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography to give the title compound (III). The single-crystal of (III) was crystallized in the mixed solvent of petroleum ether and acetone (5:1). MS: 420, m. p. 350 K.

Refinement top

All H atoms were placed in idealized positions and refined using a riding model, with C—H distances in the range 0.93–0.96 Å and with Uiso(H) = 1.2 or 1.5 times Ueq(C).

Structure description top

Coenzyme Q10 plays an essential role in the electron-transfer processes necessary for respiration, and is applied as a drug against many diseases. The title compound is the key intermediate to synthesize coenzyme Q10 via a coupling reactions with solanesyl bromide, and it was prepared by coupling tetramethoxytoluene (I) with 4-chioro-2-methyl-1-phenylsulfonyl- 2-butene (II) via Friedel-Crafts reaction.

The crystal packing of the title compound is stabilized by C—H···O contacts.

Do you wish to cite any related literature?

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).

Figures top
[Figure 1] Fig. 1. View of (III) showing 30% displacement ellipsoids (arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. Reaction scheme illustrating the preparation of the title compound.
1-[(E)-4-Benzenesulfonyl-3-methyl-but-2-enyl]-2,3,4,5- tetramethoxy-6-methylbenzene top
Crystal data top
C22H28O6SDx = 1.289 Mg m3
Mr = 420.50Melting point: 350 K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 9.8351 (6) ÅCell parameters from 5102 reflections
b = 20.5513 (14) Åθ = 2.0–28.3°
c = 10.9955 (7) ŵ = 0.18 mm1
β = 102.841 (1)°T = 184 K
V = 2166.9 (2) Å3Block, colourless
Z = 40.31 × 0.19 × 0.17 mm
F(000) = 896
Data collection top
Bruker SMART CCD area-detector
diffractometer
5102 independent reflections
Radiation source: fine-focus sealed tube3755 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.046
φ and ω scansθmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
h = 1212
Tmin = 0.945, Tmax = 0.969k = 2727
17680 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.138H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0531P)2 + 1.2576P]
where P = (Fo2 + 2Fc2)/3
5102 reflections(Δ/σ)max < 0.001
268 parametersΔρmax = 0.57 e Å3
0 restraintsΔρmin = 0.38 e Å3
Crystal data top
C22H28O6SV = 2166.9 (2) Å3
Mr = 420.50Z = 4
Monoclinic, P21/cMo Kα radiation
a = 9.8351 (6) ŵ = 0.18 mm1
b = 20.5513 (14) ÅT = 184 K
c = 10.9955 (7) Å0.31 × 0.19 × 0.17 mm
β = 102.841 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
5102 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)
3755 reflections with I > 2σ(I)
Tmin = 0.945, Tmax = 0.969Rint = 0.046
17680 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0510 restraints
wR(F2) = 0.138H-atom parameters constrained
S = 1.03Δρmax = 0.57 e Å3
5102 reflectionsΔρmin = 0.38 e Å3
268 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
xyzUiso*/Ueq
S10.29374 (6)0.26316 (3)0.94801 (4)0.03766 (15)
O10.18082 (16)0.46913 (7)0.28067 (16)0.0444 (4)
O20.04892 (17)0.42801 (8)0.10933 (13)0.0458 (4)
O30.26927 (17)0.36823 (9)0.18912 (16)0.0566 (5)
O40.24997 (19)0.34571 (9)0.43847 (18)0.0605 (5)
O50.3724 (2)0.20406 (8)0.97480 (15)0.0566 (5)
O60.25134 (18)0.29583 (8)1.04922 (13)0.0478 (4)
C10.0750 (2)0.43765 (9)0.32173 (19)0.0333 (4)
C20.0431 (2)0.41838 (10)0.23398 (18)0.0332 (4)
C30.1507 (2)0.38721 (10)0.27361 (19)0.0373 (5)
C40.1422 (2)0.37809 (10)0.4003 (2)0.0390 (5)
C50.0264 (2)0.39874 (10)0.48855 (19)0.0385 (5)
C60.0848 (2)0.42754 (10)0.44898 (19)0.0371 (5)
C70.2138 (3)0.44833 (13)0.5409 (2)0.0565 (7)
H7A0.18980.48180.59600.085*
H7B0.28130.46600.49610.085*
H7C0.25470.41080.59070.085*
C80.0224 (3)0.38985 (13)0.6256 (2)0.0549 (7)
H8A0.01810.42930.67120.066*
H8B0.11910.38520.63690.066*
C90.0612 (2)0.33153 (10)0.68133 (18)0.0371 (5)
H90.12580.31430.63720.045*
C100.0527 (2)0.30221 (10)0.78600 (17)0.0323 (4)
C110.0446 (3)0.32196 (14)0.8673 (2)0.0526 (6)
H11A0.10690.35640.82590.079*
H11B0.00970.33810.94740.079*
H11C0.10000.28430.88180.079*
C120.1445 (2)0.24476 (9)0.82806 (18)0.0357 (4)
H12A0.17590.22670.75550.043*
H12B0.08910.21080.85870.043*
C130.3925 (2)0.31897 (10)0.88015 (18)0.0346 (4)
C140.3929 (3)0.38410 (11)0.9102 (2)0.0467 (5)
H140.33800.39950.96520.056*
C150.4738 (3)0.42674 (13)0.8599 (3)0.0592 (7)
H150.47470.47170.88040.071*
C160.5532 (3)0.40439 (14)0.7800 (3)0.0561 (7)
H160.60920.43390.74590.067*
C170.5515 (3)0.33968 (13)0.7496 (2)0.0532 (6)
H170.60580.32460.69390.064*
C180.4713 (2)0.29623 (12)0.7996 (2)0.0446 (5)
H180.47040.25140.77870.054*
C190.2678 (3)0.42452 (12)0.2322 (3)0.0550 (7)
H19A0.31120.39400.29790.082*
H19B0.34050.44880.20340.082*
H19C0.21100.40030.16220.082*
C200.1450 (3)0.47747 (13)0.0544 (2)0.0572 (7)
H20A0.23900.46570.06290.086*
H20B0.14410.48170.03420.086*
H20C0.11780.51900.09680.086*
C210.2566 (3)0.30972 (14)0.1250 (3)0.0644 (7)
H21A0.19130.31610.07040.097*
H21B0.34800.29720.07470.097*
H21C0.22150.27530.18550.097*
C220.3725 (3)0.38408 (19)0.4270 (4)0.0894 (11)
H22A0.35170.42230.48110.134*
H22B0.44550.35820.45180.134*
H22C0.40460.39810.34020.134*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0501 (3)0.0356 (3)0.0260 (2)0.0065 (2)0.0059 (2)0.00566 (19)
O10.0437 (9)0.0280 (7)0.0646 (10)0.0002 (6)0.0185 (8)0.0025 (7)
O20.0567 (10)0.0515 (9)0.0292 (7)0.0154 (8)0.0092 (7)0.0090 (6)
O30.0386 (9)0.0654 (11)0.0579 (11)0.0021 (8)0.0062 (8)0.0105 (9)
O40.0560 (11)0.0553 (11)0.0759 (13)0.0043 (9)0.0269 (9)0.0145 (9)
O50.0743 (12)0.0468 (10)0.0456 (9)0.0223 (9)0.0067 (8)0.0153 (7)
O60.0669 (11)0.0515 (9)0.0271 (7)0.0007 (8)0.0147 (7)0.0006 (6)
C10.0352 (10)0.0243 (9)0.0402 (11)0.0029 (8)0.0082 (8)0.0006 (8)
C20.0383 (11)0.0330 (10)0.0273 (9)0.0084 (8)0.0051 (8)0.0040 (7)
C30.0329 (10)0.0378 (11)0.0376 (11)0.0027 (8)0.0003 (8)0.0013 (8)
C40.0412 (11)0.0351 (11)0.0427 (12)0.0047 (9)0.0135 (9)0.0070 (9)
C50.0477 (12)0.0358 (11)0.0321 (10)0.0165 (9)0.0088 (9)0.0036 (8)
C60.0398 (11)0.0320 (10)0.0350 (11)0.0088 (9)0.0018 (9)0.0056 (8)
C70.0520 (14)0.0602 (15)0.0492 (14)0.0017 (12)0.0058 (11)0.0216 (12)
C80.0729 (17)0.0610 (15)0.0325 (11)0.0353 (13)0.0157 (11)0.0078 (10)
C90.0432 (12)0.0409 (11)0.0279 (10)0.0110 (9)0.0096 (8)0.0009 (8)
C100.0332 (10)0.0353 (10)0.0281 (9)0.0033 (8)0.0058 (8)0.0031 (8)
C110.0487 (14)0.0724 (17)0.0420 (13)0.0064 (12)0.0212 (11)0.0019 (12)
C120.0477 (12)0.0295 (10)0.0313 (10)0.0061 (9)0.0117 (9)0.0004 (8)
C130.0336 (10)0.0403 (11)0.0270 (9)0.0021 (8)0.0006 (8)0.0009 (8)
C140.0501 (13)0.0432 (12)0.0501 (13)0.0005 (10)0.0181 (11)0.0081 (10)
C150.0659 (17)0.0475 (14)0.0695 (17)0.0139 (12)0.0264 (14)0.0151 (12)
C160.0503 (14)0.0646 (16)0.0561 (15)0.0209 (12)0.0175 (12)0.0114 (12)
C170.0470 (14)0.0681 (17)0.0473 (13)0.0065 (12)0.0167 (11)0.0144 (12)
C180.0494 (13)0.0469 (13)0.0375 (11)0.0007 (10)0.0097 (10)0.0105 (9)
C190.0483 (14)0.0399 (12)0.0847 (19)0.0056 (11)0.0320 (13)0.0089 (12)
C200.0610 (16)0.0620 (16)0.0449 (13)0.0159 (13)0.0037 (12)0.0211 (12)
C210.0631 (17)0.0601 (16)0.0614 (17)0.0131 (14)0.0043 (13)0.0123 (13)
C220.0576 (19)0.092 (2)0.131 (3)0.0004 (18)0.048 (2)0.020 (2)
Geometric parameters (Å, º) top
S1—O51.4348 (16)C10—C111.503 (3)
S1—O61.4385 (16)C11—H11A0.9800
S1—C131.772 (2)C11—H11B0.9800
S1—C121.783 (2)C11—H11C0.9800
O1—C11.384 (2)C12—H12A0.9900
O1—C191.435 (3)C12—H12B0.9900
O2—C21.373 (2)C13—C141.378 (3)
O2—C201.427 (3)C13—C181.382 (3)
O3—C31.376 (2)C14—C151.379 (3)
O3—C211.413 (3)C14—H140.9500
O4—C41.393 (3)C15—C161.378 (4)
O4—C221.422 (4)C15—H150.9500
C1—C21.393 (3)C16—C171.370 (4)
C1—C61.396 (3)C16—H160.9500
C2—C31.387 (3)C17—C181.383 (3)
C3—C41.390 (3)C17—H170.9500
C4—C51.388 (3)C18—H180.9500
C5—C61.396 (3)C19—H19A0.9800
C5—C81.510 (3)C19—H19B0.9800
C6—C71.497 (3)C19—H19C0.9800
C7—H7A0.9800C20—H20A0.9800
C7—H7B0.9800C20—H20B0.9800
C7—H7C0.9800C20—H20C0.9800
C8—C91.505 (3)C21—H21A0.9800
C8—H8A0.9900C21—H21B0.9800
C8—H8B0.9900C21—H21C0.9800
C9—C101.318 (3)C22—H22A0.9800
C9—H90.9500C22—H22B0.9800
C10—C121.496 (3)C22—H22C0.9800
O5—S1—O6118.16 (10)H11A—C11—H11C109.5
O5—S1—C13108.27 (11)H11B—C11—H11C109.5
O6—S1—C13107.70 (10)C10—C12—S1113.74 (14)
O5—S1—C12106.86 (11)C10—C12—H12A108.8
O6—S1—C12109.80 (10)S1—C12—H12A108.8
C13—S1—C12105.33 (9)C10—C12—H12B108.8
C1—O1—C19112.09 (15)S1—C12—H12B108.8
C2—O2—C20113.69 (17)H12A—C12—H12B107.7
C3—O3—C21114.98 (19)C14—C13—C18120.7 (2)
C4—O4—C22113.2 (2)C14—C13—S1120.01 (17)
O1—C1—C2118.63 (18)C18—C13—S1119.30 (17)
O1—C1—C6120.44 (18)C13—C14—C15119.5 (2)
C2—C1—C6120.89 (19)C13—C14—H14120.3
O2—C2—C3120.99 (18)C15—C14—H14120.3
O2—C2—C1119.57 (19)C16—C15—C14120.2 (2)
C3—C2—C1119.38 (18)C16—C15—H15119.9
O3—C3—C2120.66 (19)C14—C15—H15119.9
O3—C3—C4119.4 (2)C17—C16—C15120.0 (2)
C2—C3—C4119.84 (19)C17—C16—H16120.0
C5—C4—C3121.1 (2)C15—C16—H16120.0
C5—C4—O4119.79 (19)C16—C17—C18120.5 (2)
C3—C4—O4119.1 (2)C16—C17—H17119.8
C4—C5—C6119.35 (19)C18—C17—H17119.8
C4—C5—C8119.7 (2)C13—C18—C17119.1 (2)
C6—C5—C8121.0 (2)C13—C18—H18120.4
C5—C6—C1119.39 (19)C17—C18—H18120.4
C5—C6—C7121.0 (2)O1—C19—H19A109.5
C1—C6—C7119.6 (2)O1—C19—H19B109.5
C6—C7—H7A109.5H19A—C19—H19B109.5
C6—C7—H7B109.5O1—C19—H19C109.5
H7A—C7—H7B109.5H19A—C19—H19C109.5
C6—C7—H7C109.5H19B—C19—H19C109.5
H7A—C7—H7C109.5O2—C20—H20A109.5
H7B—C7—H7C109.5O2—C20—H20B109.5
C9—C8—C5113.14 (18)H20A—C20—H20B109.5
C9—C8—H8A109.0O2—C20—H20C109.5
C5—C8—H8A109.0H20A—C20—H20C109.5
C9—C8—H8B109.0H20B—C20—H20C109.5
C5—C8—H8B109.0O3—C21—H21A109.5
H8A—C8—H8B107.8O3—C21—H21B109.5
C10—C9—C8125.77 (19)H21A—C21—H21B109.5
C10—C9—H9117.1O3—C21—H21C109.5
C8—C9—H9117.1H21A—C21—H21C109.5
C9—C10—C12118.66 (18)H21B—C21—H21C109.5
C9—C10—C11124.6 (2)O4—C22—H22A109.5
C12—C10—C11116.71 (18)O4—C22—H22B109.5
C10—C11—H11A109.5H22A—C22—H22B109.5
C10—C11—H11B109.5O4—C22—H22C109.5
H11A—C11—H11B109.5H22A—C22—H22C109.5
C10—C11—H11C109.5H22B—C22—H22C109.5
C19—O1—C1—C279.7 (2)O1—C1—C6—C5176.67 (17)
C19—O1—C1—C6102.4 (2)C2—C1—C6—C51.1 (3)
C20—O2—C2—C373.4 (3)O1—C1—C6—C72.7 (3)
C20—O2—C2—C1109.4 (2)C2—C1—C6—C7179.49 (19)
O1—C1—C2—O23.2 (3)C4—C5—C8—C999.8 (3)
C6—C1—C2—O2178.95 (17)C6—C5—C8—C980.3 (3)
O1—C1—C2—C3179.51 (17)C5—C8—C9—C10160.8 (2)
C6—C1—C2—C31.7 (3)C8—C9—C10—C12179.7 (2)
C21—O3—C3—C279.9 (3)C8—C9—C10—C110.8 (4)
C21—O3—C3—C4103.6 (3)C9—C10—C12—S1101.1 (2)
O2—C2—C3—O33.5 (3)C11—C10—C12—S179.4 (2)
C1—C2—C3—O3179.31 (18)O5—S1—C12—C10178.22 (15)
O2—C2—C3—C4179.99 (18)O6—S1—C12—C1052.48 (17)
C1—C2—C3—C42.8 (3)C13—S1—C12—C1063.22 (17)
O3—C3—C4—C5177.67 (19)O5—S1—C13—C14141.46 (18)
C2—C3—C4—C51.1 (3)O6—S1—C13—C1412.6 (2)
O3—C3—C4—O44.5 (3)C12—S1—C13—C14104.51 (19)
C2—C3—C4—O4178.90 (19)O5—S1—C13—C1837.00 (19)
C22—O4—C4—C5107.8 (3)O6—S1—C13—C18165.83 (17)
C22—O4—C4—C374.4 (3)C12—S1—C13—C1877.03 (18)
C3—C4—C5—C61.7 (3)C18—C13—C14—C150.5 (4)
O4—C4—C5—C6176.06 (18)S1—C13—C14—C15177.9 (2)
C3—C4—C5—C8178.20 (19)C13—C14—C15—C160.1 (4)
O4—C4—C5—C84.0 (3)C14—C15—C16—C170.4 (4)
C4—C5—C6—C12.8 (3)C15—C16—C17—C180.6 (4)
C8—C5—C6—C1177.12 (18)C14—C13—C18—C170.3 (3)
C4—C5—C6—C7177.8 (2)S1—C13—C18—C17178.12 (18)
C8—C5—C6—C72.3 (3)C16—C17—C18—C130.2 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···O6i0.992.583.554 (2)168
C19—H19C···O6ii0.982.563.305 (3)133
C22—H22B···O5iii0.982.263.231 (4)171
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y, z1; (iii) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC22H28O6S
Mr420.50
Crystal system, space groupMonoclinic, P21/c
Temperature (K)184
a, b, c (Å)9.8351 (6), 20.5513 (14), 10.9955 (7)
β (°) 102.841 (1)
V3)2166.9 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.18
Crystal size (mm)0.31 × 0.19 × 0.17
Data collection
DiffractometerBruker SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Bruker, 1998)
Tmin, Tmax0.945, 0.969
No. of measured, independent and
observed [I > 2σ(I)] reflections
17680, 5102, 3755
Rint0.046
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.138, 1.03
No. of reflections5102
No. of parameters268
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.57, 0.38

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C12—H12A···O6i0.992.583.554 (2)168.0
C19—H19C···O6ii0.982.563.305 (3)133.3
C22—H22B···O5iii0.982.263.231 (4)170.5
Symmetry codes: (i) x, y+1/2, z1/2; (ii) x, y, z1; (iii) x1, y+1/2, z1/2.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds