Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100013603/da1149sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013603/da1149IIIsup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013603/da1149VIsup3.hkl |
CCDC references: 158259; 158260
Compound (III) was prepared by the Johnson orthoester Claisen rearrangement of (I) on treatment with triethylorthoacetate in toluene at reflux under nitrogen. A similar reaction using (II) furnished an ester which was reduced with lithium aluminium hydride in diethyl ether at 253–273 K to generate the alcohol (IV). Alcohol (IV) was then esterified with 4-bromobenzoyl chloride following standard methods to obtain (VI).
One C atom of the heterocyclic ring in (III) was disordered over two sites, C1 and C1*, with nonequivalent site occupancy factors of 0.58 (2) and 0.42 (2), respectively. For both compounds (III) and (VI) most of the H atoms were located from difference Fourier syntheses but these were included in the refinements at geometrically idealized positions with C—H 0.93–1.00 Å, utilizing a riding model and isotropic displacement parameters. Although the starting material for (III) was a racemic mixture of diastereomers, the final product of (III) crystallized in a non-centrosymmetric space group. However, its absolute structure could not be determined because the equivalent reflections were not collected. The Flack parameter (Flack, 1983) for the inverted structure was 0.12 (18).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988) for (III); CAD-4 Software (Enraf-Nonius, 1989) for (VI). Cell refinement: MSC/AFC Diffractometer Control Software for (III); CAD-4 Software for (VI). For both compounds, data reduction: TEXSAN (Molecular Structure Corporation, 1994); program(s) used to solve structure: SAPI91 (Fan, 1991); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: TEXSAN; software used to prepare material for publication: SHELXL97.
C19H24O3S | F(000) = 712 |
Mr = 332.44 | Dx = 1.269 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: P 2c -2n | Cell parameters from 25 reflections |
a = 10.369 (2) Å | θ = 10–15° |
b = 20.791 (3) Å | µ = 0.20 mm−1 |
c = 8.071 (3) Å | T = 170 K |
V = 1740.0 (8) Å3 | Plate, colourless |
Z = 4 | 0.52 × 0.48 × 0.14 mm |
Rigaku AFC-6S diffractometer | 1147 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.00 |
Graphite monochromator | θmax = 27.5°, θmin = 2.5° |
ω/2θ scans | h = 0→13 |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections; North et al., 1968) | k = 0→27 |
Tmin = 0.90, Tmax = 0.97 | l = 0→10 |
2150 measured reflections | 3 standard reflections every 200 reflections |
2150 independent reflections | intensity decay: <0.1% |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.140 | w = 1/[σ2(Fo2) + (0.055P)2 + 0.82P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.01 |
2150 reflections | Δρmax = 0.33 e Å−3 |
219 parameters | Δρmin = −0.28 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.05 (18) |
C19H24O3S | V = 1740.0 (8) Å3 |
Mr = 332.44 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 10.369 (2) Å | µ = 0.20 mm−1 |
b = 20.791 (3) Å | T = 170 K |
c = 8.071 (3) Å | 0.52 × 0.48 × 0.14 mm |
Rigaku AFC-6S diffractometer | 1147 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections; North et al., 1968) | Rint = 0.00 |
Tmin = 0.90, Tmax = 0.97 | 3 standard reflections every 200 reflections |
2150 measured reflections | intensity decay: <0.1% |
2150 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.140 | Δρmax = 0.33 e Å−3 |
S = 1.01 | Δρmin = −0.28 e Å−3 |
2150 reflections | Absolute structure: (Flack, 1983) |
219 parameters | Absolute structure parameter: 0.05 (18) |
1 restraint |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.93535 (13) | 0.19996 (7) | 0.76797 (19) | 0.0381 (3) | |
O1 | 0.9410 (3) | 0.09980 (18) | 0.9678 (4) | 0.0359 (9) | |
O2 | 1.4073 (3) | 0.1698 (2) | 0.4511 (5) | 0.0416 (10) | |
O3 | 1.2621 (4) | 0.2080 (2) | 0.2721 (7) | 0.0625 (13) | |
C1 | 0.8669 (12) | 0.2086 (6) | 0.9739 (14) | 0.048 (4) | 0.58 (2) |
H1A | 0.8865 | 0.2514 | 1.0210 | 0.058* | 0.58 (2) |
H1B | 0.7723 | 0.2023 | 0.9720 | 0.058* | 0.58 (2) |
C1* | 0.9642 (19) | 0.2133 (7) | 0.9860 (18) | 0.043 (5) | 0.42 (2) |
H1*1 | 1.0561 | 0.2240 | 1.0050 | 0.051* | 0.42 (2) |
H1*2 | 0.9107 | 0.2494 | 1.0265 | 0.051* | 0.42 (2) |
C2 | 0.9318 (6) | 0.1565 (3) | 1.0699 (7) | 0.0497 (16) | |
H2A | 1.0191 | 0.1707 | 1.1037 | 0.060* | |
H2B | 0.8816 | 0.1468 | 1.1712 | 0.060* | |
C3 | 0.9849 (5) | 0.1142 (2) | 0.8052 (6) | 0.0253 (12) | |
C4 | 1.1324 (4) | 0.1093 (2) | 0.7915 (6) | 0.0242 (11) | |
C5 | 1.1871 (5) | 0.1132 (3) | 0.6168 (6) | 0.0270 (12) | |
H5 | 1.2770 | 0.0958 | 0.6216 | 0.032* | |
C6 | 1.1108 (5) | 0.0698 (3) | 0.4980 (7) | 0.0320 (12) | |
H6A | 1.1405 | 0.0778 | 0.3832 | 0.038* | |
H6B | 1.1292 | 0.0243 | 0.5248 | 0.038* | |
C7 | 0.9653 (5) | 0.0810 (3) | 0.5070 (7) | 0.0382 (14) | |
H7A | 0.9206 | 0.0509 | 0.4312 | 0.046* | |
H7B | 0.9451 | 0.1255 | 0.4716 | 0.046* | |
C8 | 0.9177 (5) | 0.0703 (3) | 0.6857 (7) | 0.0351 (13) | |
H8A | 0.8236 | 0.0781 | 0.6908 | 0.042* | |
H8B | 0.9335 | 0.0251 | 0.7181 | 0.042* | |
C9 | 1.2005 (5) | 0.0950 (2) | 0.9241 (7) | 0.0301 (13) | |
H9 | 1.1525 | 0.0905 | 1.0237 | 0.036* | |
C10 | 1.3436 (5) | 0.0846 (2) | 0.9401 (7) | 0.0297 (11) | |
C11 | 1.3869 (5) | 0.0379 (3) | 1.0489 (8) | 0.0412 (14) | |
H11 | 1.3265 | 0.0130 | 1.1100 | 0.049* | |
C12 | 1.5183 (5) | 0.0271 (3) | 1.0690 (8) | 0.0450 (16) | |
H12 | 1.5468 | −0.0054 | 1.1432 | 0.054* | |
C13 | 1.6062 (5) | 0.0623 (3) | 0.9845 (8) | 0.0434 (15) | |
H13 | 1.6958 | 0.0544 | 0.9987 | 0.052* | |
C14 | 1.5649 (5) | 0.1092 (3) | 0.8785 (7) | 0.0363 (13) | |
H14 | 1.6264 | 0.1342 | 0.8197 | 0.044* | |
C15 | 1.4332 (5) | 0.1210 (2) | 0.8552 (6) | 0.0301 (11) | |
H15 | 1.4057 | 0.1539 | 0.7815 | 0.036* | |
C16 | 1.1965 (5) | 0.1821 (3) | 0.5509 (6) | 0.0324 (12) | |
H16A | 1.1098 | 0.1964 | 0.5149 | 0.039* | |
H16B | 1.2246 | 0.2108 | 0.6419 | 0.039* | |
C17 | 1.2895 (5) | 0.1891 (3) | 0.4068 (7) | 0.0341 (13) | |
C18 | 1.5085 (5) | 0.1752 (3) | 0.3257 (7) | 0.0379 (13) | |
H18A | 1.5249 | 0.2208 | 0.2983 | 0.045* | |
H18B | 1.4832 | 0.1522 | 0.2233 | 0.045* | |
C19 | 1.6257 (6) | 0.1451 (3) | 0.4004 (9) | 0.0540 (18) | |
H19A | 1.6477 | 0.1675 | 0.5034 | 0.081* | |
H19B | 1.6979 | 0.1484 | 0.3225 | 0.081* | |
H19C | 1.6084 | 0.0997 | 0.4244 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0411 (7) | 0.0432 (7) | 0.0301 (6) | 0.0125 (7) | 0.0059 (9) | 0.0007 (7) |
O1 | 0.0305 (19) | 0.053 (2) | 0.0245 (19) | −0.0032 (18) | 0.0058 (18) | 0.0061 (18) |
O2 | 0.032 (2) | 0.068 (3) | 0.025 (2) | 0.0022 (19) | 0.0057 (17) | 0.010 (2) |
O3 | 0.045 (2) | 0.110 (4) | 0.032 (2) | 0.016 (2) | 0.011 (3) | 0.031 (3) |
C1 | 0.032 (7) | 0.071 (8) | 0.042 (6) | 0.002 (5) | 0.007 (5) | −0.020 (6) |
C1* | 0.060 (13) | 0.036 (9) | 0.032 (8) | −0.002 (7) | −0.005 (8) | −0.005 (6) |
C2 | 0.049 (4) | 0.073 (4) | 0.027 (3) | 0.001 (4) | 0.006 (3) | −0.008 (3) |
C3 | 0.024 (2) | 0.026 (3) | 0.026 (3) | 0.002 (2) | 0.002 (2) | 0.006 (2) |
C4 | 0.029 (2) | 0.018 (2) | 0.026 (3) | 0.0025 (19) | 0.002 (2) | 0.002 (2) |
C5 | 0.025 (3) | 0.040 (3) | 0.016 (2) | 0.002 (2) | 0.003 (2) | 0.001 (2) |
C6 | 0.036 (3) | 0.034 (3) | 0.026 (3) | −0.001 (2) | 0.003 (2) | −0.005 (2) |
C7 | 0.036 (3) | 0.050 (4) | 0.029 (3) | −0.007 (3) | −0.006 (3) | −0.008 (3) |
C8 | 0.026 (3) | 0.045 (3) | 0.035 (3) | −0.003 (3) | 0.006 (2) | −0.005 (3) |
C9 | 0.025 (3) | 0.036 (3) | 0.029 (3) | −0.002 (2) | 0.007 (2) | 0.000 (2) |
C10 | 0.030 (3) | 0.034 (3) | 0.026 (3) | 0.003 (2) | −0.003 (2) | 0.001 (2) |
C11 | 0.037 (3) | 0.047 (3) | 0.040 (3) | −0.004 (3) | −0.005 (3) | 0.005 (3) |
C12 | 0.042 (3) | 0.050 (4) | 0.043 (4) | 0.007 (3) | −0.012 (3) | 0.016 (3) |
C13 | 0.023 (2) | 0.059 (4) | 0.048 (4) | 0.010 (3) | −0.004 (3) | −0.008 (3) |
C14 | 0.029 (3) | 0.046 (3) | 0.034 (3) | −0.002 (3) | 0.003 (3) | −0.005 (3) |
C15 | 0.030 (3) | 0.035 (3) | 0.026 (3) | −0.003 (2) | −0.008 (2) | −0.001 (2) |
C16 | 0.029 (3) | 0.046 (3) | 0.023 (3) | 0.000 (2) | 0.004 (2) | 0.004 (2) |
C17 | 0.029 (3) | 0.046 (4) | 0.027 (3) | 0.000 (2) | 0.005 (2) | 0.003 (3) |
C18 | 0.037 (3) | 0.053 (3) | 0.024 (3) | −0.006 (3) | 0.010 (2) | 0.007 (3) |
C19 | 0.038 (3) | 0.081 (5) | 0.043 (4) | 0.005 (3) | 0.007 (3) | 0.006 (4) |
S1—C1* | 1.806 (14) | C7—H7A | 0.9900 |
S1—C1 | 1.816 (11) | C7—H7B | 0.9900 |
S1—C3 | 1.880 (5) | C8—H8A | 0.9900 |
O1—C3 | 1.421 (6) | C8—H8B | 0.9900 |
O1—C2 | 1.442 (7) | C9—C10 | 1.506 (7) |
O2—C17 | 1.335 (6) | C9—H9 | 0.9500 |
O2—C18 | 1.462 (6) | C10—C15 | 1.381 (7) |
O3—C17 | 1.191 (7) | C10—C11 | 1.385 (8) |
C1—C2 | 1.491 (13) | C11—C12 | 1.390 (8) |
C1—H1A | 0.9900 | C11—H11 | 0.9500 |
C1—H1B | 0.9900 | C12—C13 | 1.352 (8) |
C1*—C2 | 1.401 (15) | C12—H12 | 0.9500 |
C1*—H1*1 | 0.9900 | C13—C14 | 1.366 (8) |
C1*—H1*2 | 0.9900 | C13—H13 | 0.9500 |
C2—H2A | 0.9900 | C14—C15 | 1.400 (7) |
C2—H2B | 0.9900 | C14—H14 | 0.9500 |
C3—C8 | 1.499 (7) | C15—H15 | 0.9500 |
C3—C4 | 1.537 (6) | C16—C17 | 1.517 (7) |
C4—C9 | 1.317 (7) | C16—H16A | 0.9900 |
C4—C5 | 1.522 (7) | C16—H16B | 0.9900 |
C5—C16 | 1.532 (7) | C18—C19 | 1.493 (8) |
C5—C6 | 1.536 (7) | C18—H18A | 0.9900 |
C5—H5 | 1.0000 | C18—H18B | 0.9900 |
C6—C7 | 1.528 (7) | C19—H19A | 0.9800 |
C6—H6A | 0.9900 | C19—H19B | 0.9800 |
C6—H6B | 0.9900 | C19—H19C | 0.9800 |
C7—C8 | 1.541 (8) | ||
C1*—S1—C1 | 32.7 (6) | C6—C7—H7B | 109.7 |
C1*—S1—C3 | 86.8 (5) | C8—C7—H7B | 109.7 |
C1—S1—C3 | 93.1 (4) | H7A—C7—H7B | 108.2 |
C3—O1—C2 | 112.1 (4) | C3—C8—C7 | 111.4 (4) |
C17—O2—C18 | 116.7 (4) | C3—C8—H8A | 109.3 |
C2—C1—S1 | 103.2 (6) | C7—C8—H8A | 109.3 |
C2—C1—H1A | 111.1 | C3—C8—H8B | 109.3 |
S1—C1—H1A | 111.1 | C7—C8—H8B | 109.3 |
C2—C1—H1B | 111.1 | H8A—C8—H8B | 108.0 |
S1—C1—H1B | 111.1 | C4—C9—C10 | 129.1 (5) |
H1A—C1—H1B | 109.1 | C4—C9—H9 | 115.4 |
C2—C1*—S1 | 107.6 (9) | C10—C9—H9 | 115.4 |
C2—C1*—H1*1 | 110.2 | C15—C10—C11 | 118.8 (5) |
S1—C1*—H1*1 | 110.2 | C15—C10—C9 | 122.8 (5) |
C2—C1*—H1*2 | 110.2 | C11—C10—C9 | 118.3 (5) |
S1—C1*—H1*2 | 110.2 | C10—C11—C12 | 120.3 (5) |
H1*1—C1*—H1*2 | 108.5 | C10—C11—H11 | 119.9 |
C1*—C2—O1 | 113.4 (7) | C12—C11—H11 | 119.9 |
C1*—C2—C1 | 41.1 (8) | C13—C12—C11 | 121.0 (5) |
O1—C2—C1 | 109.0 (6) | C13—C12—H12 | 119.5 |
C1*—C2—H2A | 70.3 | C11—C12—H12 | 119.5 |
O1—C2—H2A | 109.9 | C12—C13—C14 | 119.3 (5) |
C1—C2—H2A | 109.9 | C12—C13—H13 | 120.3 |
C1*—C2—H2B | 134.2 | C14—C13—H13 | 120.3 |
O1—C2—H2B | 109.9 | C13—C14—C15 | 121.0 (5) |
C1—C2—H2B | 109.9 | C13—C14—H14 | 119.5 |
H2A—C2—H2B | 108.3 | C15—C14—H14 | 119.5 |
O1—C3—C8 | 108.5 (4) | C10—C15—C14 | 119.5 (5) |
O1—C3—C4 | 111.8 (4) | C10—C15—H15 | 120.2 |
C8—C3—C4 | 112.1 (4) | C14—C15—H15 | 120.2 |
O1—C3—S1 | 105.0 (3) | C17—C16—C5 | 113.3 (4) |
C8—C3—S1 | 110.3 (4) | C17—C16—H16A | 108.9 |
C4—C3—S1 | 108.8 (3) | C5—C16—H16A | 108.9 |
C9—C4—C5 | 124.4 (4) | C17—C16—H16B | 108.9 |
C9—C4—C3 | 119.3 (5) | C5—C16—H16B | 108.9 |
C5—C4—C3 | 115.7 (4) | H16A—C16—H16B | 107.7 |
C4—C5—C16 | 113.3 (4) | O3—C17—O2 | 124.2 (5) |
C4—C5—C6 | 110.8 (4) | O3—C17—C16 | 125.4 (5) |
C16—C5—C6 | 111.4 (4) | O2—C17—C16 | 110.4 (4) |
C4—C5—H5 | 107.0 | O2—C18—C19 | 105.8 (5) |
C16—C5—H5 | 107.0 | O2—C18—H18A | 110.6 |
C6—C5—H5 | 107.0 | C19—C18—H18A | 110.6 |
C7—C6—C5 | 112.9 (4) | O2—C18—H18B | 110.6 |
C7—C6—H6A | 109.0 | C19—C18—H18B | 110.6 |
C5—C6—H6A | 109.0 | H18A—C18—H18B | 108.7 |
C7—C6—H6B | 109.0 | C18—C19—H19A | 109.5 |
C5—C6—H6B | 109.0 | C18—C19—H19B | 109.5 |
H6A—C6—H6B | 107.8 | H19A—C19—H19B | 109.5 |
C6—C7—C8 | 109.8 (5) | C18—C19—H19C | 109.5 |
C6—C7—H7A | 109.7 | H19A—C19—H19C | 109.5 |
C8—C7—H7A | 109.7 | H19B—C19—H19C | 109.5 |
C1*—S1—C1—C2 | −58.0 (10) | C3—C4—C5—C6 | −46.1 (6) |
C3—S1—C1—C2 | 21.2 (7) | C4—C5—C6—C7 | 50.9 (6) |
C1—S1—C1*—C2 | 67.3 (13) | C16—C5—C6—C7 | −76.1 (6) |
C3—S1—C1*—C2 | −33.5 (10) | C5—C6—C7—C8 | −57.4 (6) |
S1—C1*—C2—O1 | 25.3 (13) | O1—C3—C8—C7 | −177.3 (4) |
S1—C1*—C2—C1 | −67.2 (11) | C4—C3—C8—C7 | −53.4 (6) |
C3—O1—C2—C1* | 1.8 (11) | S1—C3—C8—C7 | 68.1 (5) |
C3—O1—C2—C1 | 45.7 (7) | C6—C7—C8—C3 | 58.3 (6) |
S1—C1—C2—C1* | 63.9 (11) | C5—C4—C9—C10 | 5.4 (9) |
S1—C1—C2—O1 | −40.2 (8) | C3—C4—C9—C10 | 176.9 (5) |
C2—O1—C3—C8 | −144.5 (4) | C4—C9—C10—C15 | 38.6 (9) |
C2—O1—C3—C4 | 91.4 (5) | C4—C9—C10—C11 | −143.5 (6) |
C2—O1—C3—S1 | −26.5 (5) | C15—C10—C11—C12 | −1.3 (9) |
C1*—S1—C3—O1 | 33.9 (7) | C9—C10—C11—C12 | −179.3 (6) |
C1—S1—C3—O1 | 1.8 (5) | C10—C11—C12—C13 | 0.6 (10) |
C1*—S1—C3—C8 | 150.7 (7) | C11—C12—C13—C14 | 0.3 (10) |
C1—S1—C3—C8 | 118.6 (5) | C12—C13—C14—C15 | −0.5 (9) |
C1*—S1—C3—C4 | −85.9 (7) | C11—C10—C15—C14 | 1.1 (8) |
C1—S1—C3—C4 | −118.0 (5) | C9—C10—C15—C14 | 179.0 (5) |
O1—C3—C4—C9 | −1.8 (7) | C13—C14—C15—C10 | −0.3 (8) |
C8—C3—C4—C9 | −123.9 (5) | C4—C5—C16—C17 | 160.5 (4) |
S1—C3—C4—C9 | 113.8 (5) | C6—C5—C16—C17 | −73.7 (5) |
O1—C3—C4—C5 | 170.5 (4) | C18—O2—C17—O3 | 2.5 (9) |
C8—C3—C4—C5 | 48.4 (6) | C18—O2—C17—C16 | −178.6 (4) |
S1—C3—C4—C5 | −73.9 (5) | C5—C16—C17—O3 | 120.7 (7) |
C9—C4—C5—C16 | −108.2 (6) | C5—C16—C17—O2 | −58.2 (6) |
C3—C4—C5—C16 | 79.9 (5) | C17—O2—C18—C19 | −174.8 (5) |
C9—C4—C5—C6 | 125.7 (5) |
C19H23BrO3S | F(000) = 848 |
Mr = 411.34 | Dx = 1.477 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
a = 7.243 (2) Å | Cell parameters from 25 reflections |
b = 11.541 (1) Å | θ = 20–30° |
c = 22.180 (5) Å | µ = 4.20 mm−1 |
β = 94.09 (2)° | T = 293 K |
V = 1849.3 (7) Å3 | Needle, colourless |
Z = 4 | 0.30 × 0.16 × 0.10 mm |
Enraf-Nonius CAD4 diffractometer | 2207 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.03 |
Graphite monochromator | θmax = 68°, θmin = 5° |
ω/2θ scans | h = 0→8 |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections; North et al., 1968) | k = 0→13 |
Tmin = 0.37, Tmax = 0.68 | l = −26→26 |
3651 measured reflections | 3 standard reflections every 200 reflections |
3372 independent reflections | intensity decay: <0.1% |
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)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0736P)2 + 2.357P] where P = (Fo2 + 2Fc2)/3 |
3372 reflections | (Δ/σ)max < 0.01 |
217 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.83 e Å−3 |
C19H23BrO3S | V = 1849.3 (7) Å3 |
Mr = 411.34 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 7.243 (2) Å | µ = 4.20 mm−1 |
b = 11.541 (1) Å | T = 293 K |
c = 22.180 (5) Å | 0.30 × 0.16 × 0.10 mm |
β = 94.09 (2)° |
Enraf-Nonius CAD4 diffractometer | 2207 reflections with I > 2σ(I) |
Absorption correction: empirical (using intensity measurements) via ψ-scan (3 reflections; North et al., 1968) | Rint = 0.03 |
Tmin = 0.37, Tmax = 0.68 | 3 standard reflections every 200 reflections |
3651 measured reflections | intensity decay: <0.1% |
3372 independent reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.164 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.43 e Å−3 |
3372 reflections | Δρmin = −0.83 e Å−3 |
217 parameters |
x | y | z | Uiso*/Ueq | ||
Br1 | 1.21939 (9) | −0.37684 (6) | −0.32880 (3) | 0.0713 (3) | |
S1 | −0.2539 (2) | −0.36685 (12) | −0.04414 (6) | 0.0555 (4) | |
O1 | −0.1207 (5) | −0.2545 (3) | 0.05246 (16) | 0.0561 (10) | |
O2 | 0.4492 (5) | −0.3296 (3) | −0.17692 (14) | 0.0468 (9) | |
O3 | 0.4897 (6) | −0.5198 (3) | −0.16423 (19) | 0.0669 (11) | |
C1 | −0.2675 (10) | −0.4330 (6) | 0.0288 (3) | 0.0734 (19) | |
H1A | −0.3885 | −0.4208 | 0.0439 | 0.088* | |
H1B | −0.2439 | −0.5156 | 0.0269 | 0.088* | |
C2 | −0.1219 (11) | −0.3739 (6) | 0.0675 (3) | 0.0740 (19) | |
H2A | −0.1458 | −0.3833 | 0.1097 | 0.089* | |
H2B | −0.0023 | −0.4079 | 0.0613 | 0.089* | |
C3 | −0.1267 (7) | −0.2373 (4) | −0.0112 (2) | 0.0428 (11) | |
C4 | 0.0595 (6) | −0.2278 (4) | −0.0373 (2) | 0.0383 (11) | |
C5 | 0.0341 (7) | −0.2095 (4) | −0.1055 (2) | 0.0425 (11) | |
H5 | −0.0458 | −0.2723 | −0.1217 | 0.051* | |
C6 | −0.0726 (7) | −0.0961 (5) | −0.1178 (3) | 0.0529 (13) | |
H6A | −0.0007 | −0.0319 | −0.1004 | 0.063* | |
H6B | −0.0903 | −0.0836 | −0.1611 | 0.063* | |
C7 | −0.2558 (7) | −0.0993 (5) | −0.0916 (3) | 0.0585 (15) | |
H7A | −0.3328 | −0.1577 | −0.1123 | 0.070* | |
H7B | −0.3165 | −0.0249 | −0.0979 | 0.070* | |
C8 | −0.2376 (7) | −0.1266 (5) | −0.0239 (3) | 0.0533 (13) | |
H8A | −0.1766 | −0.0625 | −0.0023 | 0.064* | |
H8B | −0.3599 | −0.1354 | −0.0093 | 0.064* | |
C9 | 0.2215 (7) | −0.2251 (5) | −0.0066 (2) | 0.0486 (12) | |
H9 | 0.3210 | −0.2182 | −0.0306 | 0.058* | |
C10 | 0.2766 (9) | −0.2311 (6) | 0.0602 (2) | 0.0687 (18) | |
H10A | 0.4088 | −0.2256 | 0.0666 | 0.103* | |
H10B | 0.2358 | −0.3034 | 0.0760 | 0.103* | |
H10C | 0.2202 | −0.1682 | 0.0804 | 0.103* | |
C11 | 0.2104 (7) | −0.2135 (5) | −0.1396 (2) | 0.0460 (12) | |
H11A | 0.1821 | −0.1871 | −0.1807 | 0.055* | |
H11B | 0.3012 | −0.1610 | −0.1204 | 0.055* | |
C12 | 0.2925 (7) | −0.3342 (5) | −0.1409 (2) | 0.0497 (13) | |
H12A | 0.3307 | −0.3595 | −0.1002 | 0.060* | |
H12B | 0.2014 | −0.3885 | −0.1583 | 0.060* | |
C13 | 0.5375 (7) | −0.4287 (5) | −0.1841 (2) | 0.0467 (12) | |
C14 | 0.7036 (7) | −0.4138 (4) | −0.2188 (2) | 0.0421 (11) | |
C15 | 0.8280 (8) | −0.5035 (5) | −0.2202 (2) | 0.0549 (14) | |
H15 | 0.8072 | −0.5710 | −0.1988 | 0.066* | |
C16 | 0.9834 (8) | −0.4955 (5) | −0.2526 (3) | 0.0600 (15) | |
H16 | 1.0662 | −0.5569 | −0.2541 | 0.072* | |
C17 | 1.0120 (8) | −0.3923 (5) | −0.2832 (2) | 0.0500 (13) | |
C18 | 0.8921 (8) | −0.3003 (5) | −0.2806 (2) | 0.0565 (14) | |
H18 | 0.9149 | −0.2311 | −0.3003 | 0.068* | |
C19 | 0.7390 (7) | −0.3127 (5) | −0.2487 (2) | 0.0531 (14) | |
H19 | 0.6565 | −0.2512 | −0.2472 | 0.064* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0631 (4) | 0.0805 (5) | 0.0740 (5) | 0.0032 (4) | 0.0311 (3) | −0.0040 (4) |
S1 | 0.0572 (8) | 0.0511 (8) | 0.0589 (8) | −0.0150 (7) | 0.0081 (6) | 0.0042 (7) |
O1 | 0.066 (2) | 0.062 (2) | 0.044 (2) | 0.001 (2) | 0.0207 (18) | −0.0003 (17) |
O2 | 0.054 (2) | 0.046 (2) | 0.0434 (18) | −0.0013 (17) | 0.0222 (16) | 0.0017 (15) |
O3 | 0.081 (3) | 0.043 (2) | 0.082 (3) | −0.009 (2) | 0.035 (2) | −0.002 (2) |
C1 | 0.092 (5) | 0.061 (4) | 0.071 (4) | −0.008 (4) | 0.027 (4) | 0.015 (3) |
C2 | 0.100 (5) | 0.073 (4) | 0.051 (3) | 0.011 (4) | 0.014 (3) | 0.017 (3) |
C3 | 0.043 (3) | 0.048 (3) | 0.038 (3) | −0.003 (2) | 0.009 (2) | −0.002 (2) |
C4 | 0.040 (3) | 0.038 (3) | 0.037 (2) | 0.000 (2) | 0.006 (2) | 0.001 (2) |
C5 | 0.040 (3) | 0.048 (3) | 0.039 (3) | −0.008 (2) | 0.002 (2) | 0.003 (2) |
C6 | 0.053 (3) | 0.052 (3) | 0.054 (3) | 0.000 (3) | 0.004 (3) | 0.013 (3) |
C7 | 0.045 (3) | 0.052 (3) | 0.077 (4) | 0.005 (3) | 0.002 (3) | 0.014 (3) |
C8 | 0.047 (3) | 0.048 (3) | 0.067 (3) | 0.003 (3) | 0.013 (3) | 0.000 (3) |
C9 | 0.046 (3) | 0.056 (3) | 0.043 (3) | −0.005 (2) | 0.000 (2) | −0.005 (2) |
C10 | 0.063 (4) | 0.094 (5) | 0.047 (3) | 0.004 (4) | −0.009 (3) | −0.005 (3) |
C11 | 0.048 (3) | 0.051 (3) | 0.040 (3) | −0.002 (2) | 0.011 (2) | 0.004 (2) |
C12 | 0.051 (3) | 0.056 (3) | 0.044 (3) | −0.010 (3) | 0.018 (2) | −0.001 (2) |
C13 | 0.058 (3) | 0.043 (3) | 0.041 (3) | −0.009 (2) | 0.011 (2) | −0.003 (2) |
C14 | 0.050 (3) | 0.042 (3) | 0.035 (2) | −0.001 (2) | 0.008 (2) | −0.007 (2) |
C15 | 0.067 (4) | 0.038 (3) | 0.061 (3) | −0.001 (3) | 0.016 (3) | −0.003 (3) |
C16 | 0.062 (4) | 0.050 (3) | 0.070 (4) | 0.007 (3) | 0.018 (3) | −0.009 (3) |
C17 | 0.062 (3) | 0.053 (3) | 0.035 (3) | 0.003 (3) | 0.005 (2) | −0.008 (2) |
C18 | 0.072 (4) | 0.050 (3) | 0.050 (3) | 0.011 (3) | 0.017 (3) | 0.013 (3) |
C19 | 0.055 (3) | 0.055 (3) | 0.053 (3) | 0.014 (3) | 0.026 (3) | 0.010 (3) |
Br1—C17 | 1.878 (5) | C7—H7B | 0.9700 |
S1—C1 | 1.798 (6) | C8—H8A | 0.9700 |
S1—C3 | 1.876 (5) | C8—H8B | 0.9700 |
O1—C2 | 1.418 (7) | C9—C10 | 1.507 (7) |
O1—C3 | 1.423 (6) | C9—H9 | 0.9300 |
O2—C13 | 1.325 (6) | C10—H10A | 0.9600 |
O2—C12 | 1.434 (5) | C10—H10B | 0.9600 |
O3—C13 | 1.201 (6) | C10—H10C | 0.9600 |
C1—C2 | 1.478 (9) | C11—C12 | 1.516 (7) |
C1—H1A | 0.9700 | C11—H11A | 0.9700 |
C1—H1B | 0.9700 | C11—H11B | 0.9700 |
C2—H2A | 0.9700 | C12—H12A | 0.9700 |
C2—H2B | 0.9700 | C12—H12B | 0.9700 |
C3—C4 | 1.509 (6) | C13—C14 | 1.484 (7) |
C3—C8 | 1.525 (7) | C14—C15 | 1.374 (7) |
C4—C9 | 1.314 (7) | C14—C19 | 1.376 (7) |
C4—C5 | 1.525 (6) | C15—C16 | 1.382 (7) |
C5—C11 | 1.530 (6) | C15—H15 | 0.9300 |
C5—C6 | 1.534 (7) | C16—C17 | 1.393 (8) |
C5—H5 | 0.9800 | C16—H16 | 0.9300 |
C6—C7 | 1.487 (7) | C17—C18 | 1.375 (7) |
C6—H6A | 0.9700 | C18—C19 | 1.365 (7) |
C6—H6B | 0.9700 | C18—H18 | 0.9300 |
C7—C8 | 1.531 (8) | C19—H19 | 0.9300 |
C7—H7A | 0.9700 | ||
C1—S1—C3 | 92.6 (3) | C3—C8—H8B | 109.4 |
C2—O1—C3 | 111.6 (4) | C7—C8—H8B | 109.4 |
C13—O2—C12 | 116.3 (4) | H8A—C8—H8B | 108.0 |
C2—C1—S1 | 104.1 (4) | C4—C9—C10 | 132.2 (5) |
C2—C1—H1A | 110.9 | C4—C9—H9 | 113.9 |
S1—C1—H1A | 110.9 | C10—C9—H9 | 113.9 |
C2—C1—H1B | 110.9 | C9—C10—H10A | 109.5 |
S1—C1—H1B | 110.9 | C9—C10—H10B | 109.5 |
H1A—C1—H1B | 109.0 | H10A—C10—H10B | 109.5 |
O1—C2—C1 | 109.2 (5) | C9—C10—H10C | 109.5 |
O1—C2—H2A | 109.8 | H10A—C10—H10C | 109.5 |
C1—C2—H2A | 109.8 | H10B—C10—H10C | 109.5 |
O1—C2—H2B | 109.8 | C12—C11—C5 | 112.3 (4) |
C1—C2—H2B | 109.8 | C12—C11—H11A | 109.1 |
H2A—C2—H2B | 108.3 | C5—C11—H11A | 109.1 |
O1—C3—C4 | 115.2 (4) | C12—C11—H11B | 109.1 |
O1—C3—C8 | 106.2 (4) | C5—C11—H11B | 109.1 |
C4—C3—C8 | 110.0 (4) | H11A—C11—H11B | 107.9 |
O1—C3—S1 | 104.8 (3) | O2—C12—C11 | 107.7 (4) |
C4—C3—S1 | 109.6 (3) | O2—C12—H12A | 110.2 |
C8—C3—S1 | 111.0 (4) | C11—C12—H12A | 110.2 |
C9—C4—C3 | 126.3 (4) | O2—C12—H12B | 110.2 |
C9—C4—C5 | 123.4 (4) | C11—C12—H12B | 110.2 |
C3—C4—C5 | 110.1 (4) | H12A—C12—H12B | 108.5 |
C4—C5—C11 | 116.1 (4) | O3—C13—O2 | 123.9 (5) |
C4—C5—C6 | 108.5 (4) | O3—C13—C14 | 123.9 (5) |
C11—C5—C6 | 111.4 (4) | O2—C13—C14 | 112.3 (4) |
C4—C5—H5 | 106.7 | C15—C14—C19 | 118.9 (5) |
C11—C5—H5 | 106.7 | C15—C14—C13 | 118.8 (5) |
C6—C5—H5 | 106.7 | C19—C14—C13 | 122.3 (5) |
C7—C6—C5 | 111.2 (4) | C14—C15—C16 | 121.4 (5) |
C7—C6—H6A | 109.4 | C14—C15—H15 | 119.3 |
C5—C6—H6A | 109.4 | C16—C15—H15 | 119.3 |
C7—C6—H6B | 109.4 | C15—C16—C17 | 117.7 (5) |
C5—C6—H6B | 109.4 | C15—C16—H16 | 121.1 |
H6A—C6—H6B | 108.0 | C17—C16—H16 | 121.1 |
C6—C7—C8 | 111.8 (5) | C18—C17—C16 | 121.6 (5) |
C6—C7—H7A | 109.3 | C18—C17—Br1 | 118.7 (4) |
C8—C7—H7A | 109.3 | C16—C17—Br1 | 119.7 (4) |
C6—C7—H7B | 109.3 | C19—C18—C17 | 118.7 (5) |
C8—C7—H7B | 109.3 | C19—C18—H18 | 120.7 |
H7A—C7—H7B | 107.9 | C17—C18—H18 | 120.7 |
C3—C8—C7 | 111.2 (4) | C18—C19—C14 | 121.7 (5) |
C3—C8—H8A | 109.4 | C18—C19—H19 | 119.2 |
C7—C8—H8A | 109.4 | C14—C19—H19 | 119.2 |
C3—S1—C1—C2 | −19.3 (5) | S1—C3—C8—C7 | −66.0 (5) |
C3—O1—C2—C1 | −46.7 (7) | C6—C7—C8—C3 | −53.6 (6) |
S1—C1—C2—O1 | 39.6 (6) | C3—C4—C9—C10 | 0.6 (10) |
C2—O1—C3—C4 | −91.7 (6) | C5—C4—C9—C10 | 174.3 (6) |
C2—O1—C3—C8 | 146.4 (5) | C4—C5—C11—C12 | 69.2 (6) |
C2—O1—C3—S1 | 28.8 (5) | C6—C5—C11—C12 | −165.9 (5) |
C1—S1—C3—O1 | −4.2 (4) | C13—O2—C12—C11 | −178.9 (4) |
C1—S1—C3—C4 | 119.9 (4) | C5—C11—C12—O2 | 176.4 (4) |
C1—S1—C3—C8 | −118.4 (4) | C12—O2—C13—O3 | 2.8 (7) |
O1—C3—C4—C9 | −5.5 (7) | C12—O2—C13—C14 | −176.6 (4) |
C8—C3—C4—C9 | 114.4 (6) | O3—C13—C14—C15 | −11.5 (8) |
S1—C3—C4—C9 | −123.4 (5) | O2—C13—C14—C15 | 167.9 (5) |
O1—C3—C4—C5 | −179.9 (4) | O3—C13—C14—C19 | 169.8 (6) |
C8—C3—C4—C5 | −60.0 (5) | O2—C13—C14—C19 | −10.8 (7) |
S1—C3—C4—C5 | 62.2 (4) | C19—C14—C15—C16 | −2.3 (8) |
C9—C4—C5—C11 | 12.9 (7) | C13—C14—C15—C16 | 178.8 (5) |
C3—C4—C5—C11 | −172.6 (4) | C14—C15—C16—C17 | 1.2 (8) |
C9—C4—C5—C6 | −113.6 (5) | C15—C16—C17—C18 | 1.0 (9) |
C3—C4—C5—C6 | 61.0 (5) | C15—C16—C17—Br1 | −179.3 (4) |
C4—C5—C6—C7 | −58.7 (6) | C16—C17—C18—C19 | −2.0 (9) |
C11—C5—C6—C7 | 172.2 (5) | Br1—C17—C18—C19 | 178.4 (4) |
C5—C6—C7—C8 | 55.4 (6) | C17—C18—C19—C14 | 0.7 (9) |
O1—C3—C8—C7 | −179.3 (4) | C15—C14—C19—C18 | 1.4 (8) |
C4—C3—C8—C7 | 55.4 (6) | C13—C14—C19—C18 | −179.9 (5) |
Experimental details
(III) | (VI) | |
Crystal data | ||
Chemical formula | C19H24O3S | C19H23BrO3S |
Mr | 332.44 | 411.34 |
Crystal system, space group | Orthorhombic, Pna21 | Monoclinic, P21/n |
Temperature (K) | 170 | 293 |
a, b, c (Å) | 10.369 (2), 20.791 (3), 8.071 (3) | 7.243 (2), 11.541 (1), 22.180 (5) |
α, β, γ (°) | 90, 90, 90 | 90, 94.09 (2), 90 |
V (Å3) | 1740.0 (8) | 1849.3 (7) |
Z | 4 | 4 |
Radiation type | Mo Kα | Cu Kα |
µ (mm−1) | 0.20 | 4.20 |
Crystal size (mm) | 0.52 × 0.48 × 0.14 | 0.30 × 0.16 × 0.10 |
Data collection | ||
Diffractometer | Rigaku AFC-6S diffractometer | Enraf-Nonius CAD4 diffractometer |
Absorption correction | Empirical (using intensity measurements) via ψ-scan (3 reflections; North et al., 1968) | Empirical (using intensity measurements) via ψ-scan (3 reflections; North et al., 1968) |
Tmin, Tmax | 0.90, 0.97 | 0.37, 0.68 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2150, 2150, 1147 | 3651, 3372, 2207 |
Rint | 0.00 | 0.03 |
(sin θ/λ)max (Å−1) | 0.650 | 0.601 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.140, 1.01 | 0.054, 0.164, 1.04 |
No. of reflections | 2150 | 3372 |
No. of parameters | 219 | 217 |
No. of restraints | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.28 | 0.43, −0.83 |
Absolute structure | (Flack, 1983) | ? |
Absolute structure parameter | 0.05 (18) | ? |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), CAD-4 Software (Enraf-Nonius, 1989), MSC/AFC Diffractometer Control Software, CAD-4 Software, TEXSAN (Molecular Structure Corporation, 1994), SAPI91 (Fan, 1991), SHELXL97 (Sheldrick, 1997), TEXSAN, SHELXL97.
S1—C1* | 1.806 (14) | O1—C2 | 1.442 (7) |
S1—C1 | 1.816 (11) | O2—C17 | 1.335 (6) |
S1—C3 | 1.880 (5) | O2—C18 | 1.462 (6) |
O1—C3 | 1.421 (6) | O3—C17 | 1.191 (7) |
C1*—S1—C3 | 86.8 (5) | C3—O1—C2 | 112.1 (4) |
C1—S1—C3 | 93.1 (4) | C17—O2—C18 | 116.7 (4) |
Br1—C17 | 1.878 (5) | O1—C3 | 1.423 (6) |
S1—C1 | 1.798 (6) | O2—C13 | 1.325 (6) |
S1—C3 | 1.876 (5) | O2—C12 | 1.434 (5) |
O1—C2 | 1.418 (7) | O3—C13 | 1.201 (6) |
C1—S1—C3 | 92.6 (3) | C13—O2—C12 | 116.3 (4) |
C2—O1—C3 | 111.6 (4) |
In studies of 1,3-diastereoface selection under Johnson orthoester Claisen rearrangement conditions, we have reacted (1-oxa-4-thiaspiro[4.5]dec-6-en-6-yl)(phenyl)methanol, (I) and (1-oxa-4-thiaspiro[4.5]dec-6-en-6-yl)(methyl)methanol, (II) with triethyl orthoacetate. Whereas (I) furnished a single product identified as ethyl 6-benzylidene-1-oxa-4-thiaspiro[4.5]decane-7-acetate, (III), (II) furnished a mixture of two products which were inseparable by routine chromatographic techniques. However, the corresponding alcohols, obtained on LiAlH4 reduction in Et2O, separated well by radial chromatography. The more polar alcohol was identified, from its 4-bromobenzoate ester derivative, as 2-(6-ethylidene-1-oxa-4-thiaspiro[4.5]decan-7-yl)ethanol, (IV). Since (IV) is a consequence of rearrangement anti to the acetal sulfur, the less polar alcohol must, therefore, be a product of rearrangement syn to the acetal sulfur and possess the stereostructure shown for (V). Compound (III) is also a consequence of rearrangement syn to the acetal sulfur. The difference in the olefin geometry of (IV) from that of (III) and (V) must be noted. In this paper, we describe the crystal structures of (III) and of the 4-bromobenzoate ester of (IV), (VI). \sch
The structures of (III) and (VI) are presented in Figs. 1 and 2, respectively, and are composed of independent molecules separated by normal van der Waals distances. One C atom of the heterocyclic ring in (III) is disordered over two sites, C1 and C1*, with nonequivalent site occupancy factors of 0.58 (2) and 0.42 (2), respectively, indicating the presence of two conformations of the five-membered ring. It is interesting to note that in (III), as a result of the disorder, the rings S1/C1/C2/O1/C3 and S1/C1*/C2/O1/C3 adopt C2- and S1-envelope conformations, with atoms S1 and C2 0.773 (19) and 0.554 (11) Å, respectively, out of the planes of the remaining ring atoms [maximum deviations 0.009 (5) and 0.014 (4) Å, respectively]. The corresponding heterocyclic ring in (VI) adopts a C2-envelope conformation, with C2 0.542 (9) Å out of the plane formed by the remaining ring atoms [maximium deviation 0.030 (3) Å for C3]. In both structures the six-membered ring C3—C8 adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) Q = 0.539 (6) and 0.590 (6) Å, and θ = 171.0 (6) and 5.1 (6) and ϕ = 69 (4) and 83 (6)°, in (III) and (VI), respectively. The phenyl rings in both the structures are essentially planar.
The bond distances and angles in the two structures are normal and agree well with the corresponding values reported for similar compounds in the Cambridge Structural Database (Allen & Kennard, 1993). The S—Csp3 bond distances, although significantly different from each other in (III) [1.880 (5) Å for S—C3, and a mean of 1.811 (5) Å for S—C1 and S—C1*], are in excellent agreement with the corresponding bond distances in (VI) [1.878 (5) and 1.798 (6) Å]. Similar nonequivalent S—C bond distances have been reported in the crystal structures of cyclohexanespiro-2'-(1',3'-oxathiolan-5'-one 3'-oxide) (Frechina et al., 1992), (+)-(3S,4R)-6-phenyl-1-oxa-4-thiaspiro[4.5]decan-8-one (Sonoda et al., 1992), two derivatives of an oxa-thia-spiro-decene (Parvez et al., 1997) and 2-(7-ethylidene-6-methyl-1-oxa-4-thiaspiro[4.5]dec-7-yl)ethanol (Parvez et al., 1998).