Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106018336/hj3010sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106018336/hj30104bsup2.hkl |
CCDC reference: 616148
1R(S),2S(R),3S(R),4R(S),5R(S),6S(R)-3,4-Dichloro-7,8-dioxatricyclo[4.2.2.02,5]-dec-9-ene, (2) (Gözel et al., 1991), was prepared as follows. To a stirred solution of the dichlorodiene (1) (Reppe et al., 1948) (3.0 g, 17 mmol) in CCl4 (100 ml) was added tetraphenylporphyrin (TPP; 30 mg). The resulting mixture was irradiated with a projection lamp (500 W) while oxygen was passed through the solution, and the mixture was stirred at room temperature for 8 h. Evaporation of the solvent (303 K, 20 mm H g; 1 mm H g = 133.322 Pa) and chromatography of the residue on a silica-gel column (50 g) eluted with hexane–CH2Cl2 (1:1) gave pure endoperoxide, (2) (2.67 g, 75%, m.p. 364–365 K). The compound was recrystallized from CHCl3–hexane (Ratio?). Analysis, found: C 46.17, H 3.95%; C16H20Cl2O8 requires: C 46.41, H 3.89%. Spectroscopic analysis: IR (KBr, νmax, cm−1): 3469, 3079, 3016, 2979, 1369, 1331, 1296, 1266, 1250, 1026, 958; 1H NMR (200 MHz, CDCl3, δ, p.p.m.): 6.88 (quasi dd, J = 4.4 and 1.0 Hz, 2H, C═CH), 4.90 (m, 2H, CH—O), 4.13 (d, 2H, J = 3.5 Hz, CH—Cl), 3.37 (m, 2H); 13C NMR (50 MHz, CDCl3, δ, p.p.m.): 134.6, 72.9, 57.3, 45.1.
1R(S),2S(R),5R(S),6S(R),7S(R),8R(S)-7,8-Dichlorobicyclo[4.2.0]oct-3-ene-2,5-diol, (3a), was prepared as follows. To a magnetically stirred slurry of thiourea (0.44 g, 5.79 mmol) in methanol (30 ml) was added a solution of endoperoxide (2) (1.20 g, 5.79 mmol) in CHCl3 (30 ml) at room temperature. After completion of the addition (ca 10 min), the mixture was stirred for 1 h and the solid was removed by filtration. Evaporation of the solvent gave diol (3a) (1.15 g, 95%) as a colourless oil. Spectroscopic analysis: 1H NMR (200 MHz, CD3OD, δ, p.p.m.): 5.81 (s, 2H, C═CH), 4.51 (dd, 2H, J = 3.0 and 1.2 Hz, CH—O), 4.11 (m, 2H, CH—Cl), 2.69 (m, 2H, CH); 13C NMR (50 MHz, CD3OD, δ, p.p.m.): 134.8,68.8, 62.0, 50.9.
1R(S),2S(R),5R(S),6S(R),7S(R),8R(S)-5-(Acetyloxy)-7,8-dichlorobicyclo[4.2.0]-oct-3-en-2-yl acetate, (3b), was prepared as follows. Diol (3a) (0.81 g, 3.87 mmol) was dissolved in acetyl chloride (10 ml) and the resulting solution was stirred at room temperature overnight. The excess of unreacted acetyl chloride was evaporated (333 K, 20 mm H g). The residue was dissolved in CHCl3 and filtered through silica gel. Evaporation of the solvent gave (3b) (1.08 g, 94%, m.p. 327–328 K). The compound was recrystallized from CHCl3–hexane (Ratio?). Analysis, found: C 49.65, H 5.08%; C12H14Cl2O4 requires: C 49.17, H 4.81%. Spectroscopic analysis: IR (KBr, νmax, cm−1): 3020, 2969, 2935, 1731, 1434, 1373, 1234, 1029, 917, 755; 1H NMR (200 MHz, CDCl3, δ, p.p.m.): 5.92 (s, 2H, C═CH), 5.18 (br s, 2H, CH—O), 4.44 (d, 2H, J = 4.5 Hz, CH—Cl), 2.88 (m, 2H, CH), 2.07 (s, 6H, CH3); 13C NMR (50 MHz, CDCl3, δ, p.p.m.): 172.2, 130.9, 68.9 60.4, 46.5, 22.9.
1S(R),2S(R),3S(R),4R(S),5R(S),6R(S),7S(R),8R(S)-2,4,5-Tris(acetyloxy)-7,8-dichlorobicyclo[4.2.0]oct-3-yl acetate, (4b), and 1S(R),2S(R),3R(S),4S(R),5R(S),6R(S),7S(R),8R(S)-2,4,5-Tris(acetyloxy)-7,8-dichlorobicyclo[4.2.0]oct-3-yl acetate, (5b) (Kelebekli et al., 2005), were prepared as follows. To a stirred solution of dichlorodiacetate (3b) (0.55 g, 1.88 mmol) in EtOH (50 ml) was added a solution of KMnO4 (0.3 g, 1.88 mmol) and MgSO4 (0.23 g, 1.88 mmol) in water (20 ml) at 263 K over a period of 5 h. After completeion of the addition, the reaction mixture was stirred for an additional 15 h at 268 K and then filtered. The precipitate was washed several times with hot water. The combined filtrates were concentrated to 20 ml by rotary evaporation (333 K, 20 mm H g). The aqueous solution was extracted with ethyl acetate (3 × 75 ml) and the extracts were dried (Na2SO4). After removal of the solvent, the crude mixture was acetylated as described above to give compounds (5b) and (4b) in a ratio of 1:1 (according to 1H NMR) (0.59 g, 77%). Compounds (4b) and (5b) were separated by recrystallization from hexane–CH2Cl2 (Ratio?). The title compound, (4b), formed colourless crystals from hexane–CH2Cl2 (Ratio?) (m.p. 444–446 K). Analysis, found: C 46.68, H 4.87%; C16H20Cl2O8 requires: C 46.73, H 4.90%. Spectroscopic analysis: IR (KBr, νmax, cm−1): 3025, 2979, 2948, 1751, 1431, 1370, 1235, 1081, 1041, 758; 1H NMR (200 MHz, CDCl3, δ, p.p.m.): 5.30–5.20 (m, 4H, –CHO), 4.55 (m, 2H, –CHCl), 3.05 (m, 2H, –CH), 2.05 (s, 6H, CH3), 2.03 (s, 6H, –CH3); 13C NMR (50 MHz, CDCl3, δ, p.p.m.): 171.8, 171.6, 70.1, 69.7, 59.0, 47.0, 22.6, 22.5.
Methyl atoms were treated as riding, with C—H = 0.96 Å and with Uiso(H) = 1.5Ueq(C). [Please check added text] All other H atoms were located in a difference synthesis and refined isotropically [C—H = 0.89 (3)–1.00 (2) Å].
Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C16H20Cl2O8 | Z = 2 |
Mr = 411.22 | F(000) = 428 |
Triclinic, P1 | Dx = 1.458 Mg m−3 |
Hall symbol: -P1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9489 (5) Å | Cell parameters from 7762 reflections |
b = 11.0230 (8) Å | θ = 2.5–33.2° |
c = 11.2885 (7) Å | µ = 0.39 mm−1 |
α = 111.427 (2)° | T = 295 K |
β = 98.281 (1)° | Block, white |
γ = 108.834 (1)° | 0.32 × 0.21 × 0.20 mm |
V = 936.70 (10) Å3 |
Rigaku R-AXIS RAPID S diffractometer | 6532 reflections with I > 2σ(I) |
oscillation scans | Rint = 0.045 |
Absorption correction: multi-scan (Blessing, 1995) | θmax = 33.2°, θmin = 2.2° |
Tmin = 0.909, Tmax = 0.926 | h = −13→13 |
64683 measured reflections | k = −16→16 |
7145 independent reflections | l = −17→17 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.076 | w = 1/[σ2(Fo2) + (0.0595P)2 + 0.3756P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.190 | (Δ/σ)max = 0.002 |
S = 1.32 | Δρmax = 0.33 e Å−3 |
7145 reflections | Δρmin = −0.26 e Å−3 |
271 parameters |
C16H20Cl2O8 | γ = 108.834 (1)° |
Mr = 411.22 | V = 936.70 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.9489 (5) Å | Mo Kα radiation |
b = 11.0230 (8) Å | µ = 0.39 mm−1 |
c = 11.2885 (7) Å | T = 295 K |
α = 111.427 (2)° | 0.32 × 0.21 × 0.20 mm |
β = 98.281 (1)° |
Rigaku R-AXIS RAPID S diffractometer | 7145 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) | 6532 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 0.926 | Rint = 0.045 |
64683 measured reflections |
R[F2 > 2σ(F2)] = 0.076 | 0 restraints |
wR(F2) = 0.190 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.32 | Δρmax = 0.33 e Å−3 |
7145 reflections | Δρmin = −0.26 e Å−3 |
271 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.4965 (2) | 0.61022 (19) | 0.77019 (17) | 0.0309 (3) | |
C2 | 0.4544 (2) | 0.4592 (2) | 0.75323 (18) | 0.0330 (3) | |
C3 | 0.2891 (2) | 0.3968 (2) | 0.7761 (2) | 0.0360 (4) | |
C4 | 0.1506 (2) | 0.4225 (2) | 0.69984 (19) | 0.0356 (4) | |
C5 | 0.1919 (2) | 0.5522 (2) | 0.67124 (18) | 0.0334 (3) | |
C6 | 0.3678 (2) | 0.60502 (19) | 0.66193 (17) | 0.0314 (3) | |
C7 | 0.1893 (3) | 0.2346 (2) | 0.6858 (2) | 0.0447 (4) | |
C8 | 0.1028 (2) | 0.2742 (2) | 0.5867 (2) | 0.0430 (4) | |
C9 | 0.6381 (3) | 0.3577 (2) | 0.8030 (2) | 0.0423 (4) | |
C10 | 0.7875 (3) | 0.3840 (3) | 0.9028 (3) | 0.0567 (6) | |
C11 | 0.5991 (2) | 0.8355 (2) | 0.96058 (19) | 0.0388 (4) | |
C12 | 0.5772 (4) | 0.9116 (3) | 1.0926 (2) | 0.0553 (6) | |
C13 | 0.0206 (3) | 0.6635 (2) | 0.7595 (2) | 0.0463 (5) | |
C14 | 0.0142 (3) | 0.7843 (3) | 0.8721 (3) | 0.0739 (9) | |
C15 | 0.5351 (3) | 0.7849 (2) | 0.61363 (18) | 0.0380 (4) | |
C16 | 0.5744 (3) | 0.9313 (3) | 0.6258 (3) | 0.0543 (6) | |
Cl1 | 0.05627 (9) | 0.15421 (8) | 0.76460 (9) | 0.0702 (2) | |
Cl2 | −0.10859 (8) | 0.17212 (8) | 0.49481 (9) | 0.0731 (2) | |
O1 | 0.58777 (17) | 0.46418 (16) | 0.84715 (14) | 0.0399 (3) | |
O2 | 0.5674 (3) | 0.2543 (2) | 0.6982 (2) | 0.0718 (6) | |
O3 | 0.49473 (16) | 0.69586 (14) | 0.90194 (12) | 0.0343 (3) | |
O4 | 0.6945 (2) | 0.88949 (18) | 0.91157 (17) | 0.0556 (4) | |
O5 | 0.17410 (16) | 0.66642 (15) | 0.77633 (14) | 0.0384 (3) | |
O6 | −0.0960 (2) | 0.5712 (2) | 0.6667 (2) | 0.0735 (6) | |
O7 | 0.40837 (17) | 0.74260 (14) | 0.66243 (14) | 0.0364 (3) | |
O8 | 0.6049 (2) | 0.71054 (18) | 0.56760 (16) | 0.0477 (4) | |
H1 | 0.603 (3) | 0.648 (2) | 0.761 (2) | 0.030 (5)* | |
H10A | 0.7554 | 0.3623 | 0.9728 | 0.085* | |
H10B | 0.863 | 0.4824 | 0.9397 | 0.085* | |
H10C | 0.8402 | 0.3243 | 0.8603 | 0.085* | |
H12A | 0.6503 | 1.0109 | 1.1315 | 0.083* | |
H12B | 0.6024 | 0.8708 | 1.1506 | 0.083* | |
H12C | 0.4649 | 0.9021 | 1.0803 | 0.083* | |
H14A | −0.0098 | 0.8477 | 0.8403 | 0.111* | |
H14B | 0.119 | 0.8352 | 0.9401 | 0.111* | |
H14C | −0.0708 | 0.7477 | 0.9085 | 0.111* | |
H16A | 0.6382 | 0.947 | 0.5672 | 0.082* | |
H16B | 0.6368 | 0.9997 | 0.716 | 0.082* | |
H16C | 0.4735 | 0.9419 | 0.6019 | 0.082* | |
H2 | 0.460 (3) | 0.405 (3) | 0.662 (2) | 0.037 (6)* | |
H3 | 0.306 (3) | 0.426 (3) | 0.872 (3) | 0.044 (6)* | |
H4 | 0.066 (3) | 0.414 (3) | 0.743 (2) | 0.040 (6)* | |
H5 | 0.111 (3) | 0.525 (3) | 0.586 (3) | 0.045 (6)* | |
H6 | 0.368 (3) | 0.537 (2) | 0.575 (2) | 0.031 (5)* | |
H7 | 0.246 (3) | 0.172 (3) | 0.654 (2) | 0.042 (6)* | |
H8 | 0.157 (3) | 0.272 (3) | 0.526 (2) | 0.043 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0288 (7) | 0.0342 (8) | 0.0293 (7) | 0.0153 (6) | 0.0097 (6) | 0.0109 (6) |
C2 | 0.0306 (7) | 0.0367 (8) | 0.0322 (8) | 0.0175 (7) | 0.0087 (6) | 0.0128 (7) |
C3 | 0.0357 (8) | 0.0364 (9) | 0.0397 (9) | 0.0178 (7) | 0.0138 (7) | 0.0170 (7) |
C4 | 0.0303 (7) | 0.0372 (9) | 0.0404 (9) | 0.0164 (7) | 0.0143 (7) | 0.0144 (7) |
C5 | 0.0311 (7) | 0.0365 (8) | 0.0325 (8) | 0.0179 (7) | 0.0088 (6) | 0.0117 (7) |
C6 | 0.0326 (7) | 0.0343 (8) | 0.0304 (8) | 0.0173 (7) | 0.0108 (6) | 0.0137 (7) |
C7 | 0.0382 (9) | 0.0355 (9) | 0.0614 (13) | 0.0159 (8) | 0.0214 (9) | 0.0191 (9) |
C8 | 0.0308 (8) | 0.0382 (10) | 0.0479 (11) | 0.0103 (7) | 0.0101 (8) | 0.0104 (8) |
C9 | 0.0411 (10) | 0.0470 (11) | 0.0485 (11) | 0.0255 (9) | 0.0149 (8) | 0.0237 (9) |
C10 | 0.0444 (11) | 0.0725 (16) | 0.0654 (15) | 0.0354 (12) | 0.0124 (10) | 0.0342 (13) |
C11 | 0.0385 (9) | 0.0352 (9) | 0.0370 (9) | 0.0157 (7) | 0.0079 (7) | 0.0107 (7) |
C12 | 0.0708 (16) | 0.0443 (12) | 0.0393 (11) | 0.0212 (11) | 0.0183 (10) | 0.0080 (9) |
C13 | 0.0326 (9) | 0.0477 (11) | 0.0588 (12) | 0.0223 (8) | 0.0154 (8) | 0.0177 (10) |
C14 | 0.0474 (13) | 0.0565 (15) | 0.097 (2) | 0.0285 (12) | 0.0269 (14) | 0.0039 (15) |
C15 | 0.0428 (9) | 0.0437 (10) | 0.0325 (8) | 0.0201 (8) | 0.0151 (7) | 0.0183 (8) |
C16 | 0.0671 (15) | 0.0442 (12) | 0.0623 (14) | 0.0233 (11) | 0.0318 (12) | 0.0291 (11) |
Cl1 | 0.0631 (4) | 0.0624 (4) | 0.1061 (6) | 0.0247 (3) | 0.0432 (4) | 0.0528 (4) |
Cl2 | 0.0371 (3) | 0.0549 (4) | 0.0883 (5) | 0.0043 (2) | −0.0033 (3) | 0.0119 (3) |
O1 | 0.0394 (7) | 0.0447 (7) | 0.0364 (7) | 0.0250 (6) | 0.0060 (5) | 0.0139 (6) |
O2 | 0.0830 (14) | 0.0575 (11) | 0.0653 (12) | 0.0481 (11) | 0.0000 (10) | 0.0083 (9) |
O3 | 0.0349 (6) | 0.0345 (6) | 0.0300 (6) | 0.0146 (5) | 0.0111 (5) | 0.0098 (5) |
O4 | 0.0546 (9) | 0.0407 (8) | 0.0522 (9) | 0.0061 (7) | 0.0211 (8) | 0.0101 (7) |
O5 | 0.0306 (6) | 0.0404 (7) | 0.0406 (7) | 0.0192 (5) | 0.0103 (5) | 0.0100 (6) |
O6 | 0.0353 (8) | 0.0773 (13) | 0.0762 (13) | 0.0265 (9) | 0.0035 (8) | 0.0027 (10) |
O7 | 0.0384 (6) | 0.0381 (7) | 0.0407 (7) | 0.0207 (6) | 0.0167 (5) | 0.0193 (6) |
O8 | 0.0563 (9) | 0.0538 (9) | 0.0487 (8) | 0.0308 (8) | 0.0313 (7) | 0.0257 (7) |
C1—H1 | 0.95 (2) | C12—H12C | 0.96 |
C2—C1 | 1.514 (3) | C13—C14 | 1.492 (3) |
C2—C3 | 1.520 (3) | C14—H14A | 0.96 |
C2—H2 | 1.00 (2) | C14—H14B | 0.96 |
C3—C4 | 1.567 (3) | C14—H14C | 0.96 |
C3—C7 | 1.552 (3) | C15—C16 | 1.485 (3) |
C3—H3 | 0.99 (3) | C16—H16A | 0.96 |
C4—C8 | 1.534 (3) | C16—H16B | 0.96 |
C4—H4 | 0.96 (2) | C16—H16C | 0.96 |
C5—C4 | 1.522 (3) | Cl1—C7 | 1.788 (2) |
C5—C6 | 1.526 (2) | Cl2—C8 | 1.769 (2) |
C5—H5 | 1.00 (3) | O1—C2 | 1.450 (2) |
C6—C1 | 1.525 (2) | O1—C9 | 1.344 (2) |
C6—H6 | 0.99 (2) | O2—C9 | 1.197 (3) |
C7—C8 | 1.538 (3) | O3—C1 | 1.447 (2) |
C7—H7 | 0.98 (3) | O3—C11 | 1.353 (2) |
C8—H8 | 0.89 (3) | O4—C11 | 1.199 (3) |
C9—C10 | 1.489 (3) | O5—C13 | 1.348 (2) |
C10—H10A | 0.96 | O5—C5 | 1.453 (2) |
C10—H10B | 0.96 | O6—C13 | 1.201 (3) |
C10—H10C | 0.96 | O7—C15 | 1.354 (2) |
C11—C12 | 1.497 (3) | O7—C6 | 1.439 (2) |
C12—H12A | 0.96 | O8—C15 | 1.202 (2) |
C12—H12B | 0.96 | ||
C1—C2—C3 | 111.84 (14) | C13—C14—H14C | 109.5 |
C1—C2—H2 | 105.7 (14) | C13—O5—C5 | 115.46 (15) |
C1—C6—C5 | 114.24 (14) | C15—C16—H16A | 109.5 |
C1—C6—H6 | 107.0 (13) | C15—C16—H16B | 109.5 |
C2—C1—C6 | 107.87 (14) | C15—C16—H16C | 109.5 |
C2—C1—H1 | 109.8 (13) | C15—O7—C6 | 115.49 (14) |
C2—C3—C4 | 112.11 (15) | Cl1—C7—H7 | 105.0 (15) |
C2—C3—C7 | 114.09 (15) | Cl2—C8—H8 | 105.7 (17) |
C2—C3—H3 | 109.3 (15) | O1—C2—C1 | 107.03 (14) |
C3—C2—H2 | 114.2 (14) | O1—C2—C3 | 111.15 (15) |
C3—C4—H4 | 106.9 (14) | O1—C2—H2 | 106.5 (13) |
C3—C7—Cl1 | 110.86 (15) | O1—C9—C10 | 111.2 (2) |
C3—C7—H7 | 120.7 (15) | O2—C9—C10 | 125.4 (2) |
C4—C3—H3 | 117.5 (15) | O2—C9—O1 | 123.35 (19) |
C4—C5—C6 | 111.59 (14) | O3—C1—C2 | 108.45 (14) |
C4—C5—H5 | 108.2 (15) | O3—C1—C6 | 111.42 (13) |
C4—C8—C7 | 89.45 (16) | O3—C1—H1 | 109.6 (13) |
C4—C8—Cl2 | 117.74 (14) | O3—C11—C12 | 110.73 (18) |
C4—C8—H8 | 115.2 (17) | O4—C11—C12 | 125.4 (2) |
C5—C4—C3 | 121.16 (15) | O4—C11—O3 | 123.87 (18) |
C5—C4—C8 | 120.03 (17) | O5—C13—C14 | 111.6 (2) |
C5—C4—H4 | 111.6 (14) | O5—C5—C4 | 109.55 (15) |
C5—C6—H6 | 107.4 (13) | O5—C5—C6 | 109.17 (15) |
C6—C1—H1 | 109.6 (13) | O5—C5—H5 | 108.1 (15) |
C6—C5—H5 | 110.1 (15) | O6—C13—C14 | 125.2 (2) |
C7—C3—C4 | 87.73 (15) | O6—C13—O5 | 123.1 (2) |
C7—C3—H3 | 114.9 (15) | O7—C15—C16 | 111.57 (17) |
C7—C8—Cl2 | 121.08 (16) | O7—C6—C1 | 111.41 (14) |
C7—C8—H8 | 107.2 (16) | O7—C6—C5 | 107.94 (13) |
C8—C4—C3 | 87.36 (14) | O7—C6—H6 | 108.6 (13) |
C8—C4—H4 | 106.8 (15) | O8—C15—C16 | 125.86 (19) |
C8—C7—C3 | 87.74 (15) | O8—C15—O7 | 122.57 (18) |
C8—C7—Cl1 | 113.82 (15) | H10A—C10—H10B | 109.5 |
C8—C7—H7 | 118.4 (15) | H10A—C10—H10C | 109.5 |
C9—C10—H10A | 109.5 | H10B—C10—H10C | 109.5 |
C9—C10—H10B | 109.5 | H12A—C12—H12B | 109.5 |
C9—C10—H10C | 109.5 | H12A—C12—H12C | 109.5 |
C9—O1—C2 | 116.51 (15) | H12B—C12—H12C | 109.5 |
C11—C12—H12A | 109.5 | H14A—C14—H14B | 109.5 |
C11—C12—H12B | 109.5 | H14A—C14—H14C | 109.5 |
C11—C12—H12C | 109.5 | H14B—C14—H14C | 109.5 |
C11—O3—C1 | 116.81 (14) | H16A—C16—H16B | 109.5 |
C13—C14—H14A | 109.5 | H16A—C16—H16C | 109.5 |
C13—C14—H14B | 109.5 | H16B—C16—H16C | 109.5 |
C1—C2—C3—C4 | 47.1 (2) | C6—C5—C4—C3 | 27.2 (2) |
C1—C2—C3—C7 | 144.89 (17) | C6—C5—C4—C8 | −79.5 (2) |
C1—O3—C11—C12 | 177.04 (17) | C6—O7—C15—C16 | −176.54 (18) |
C1—O3—C11—O4 | −2.4 (3) | C6—O7—C15—O8 | 3.1 (3) |
C2—C3—C4—C5 | −29.4 (2) | C7—C3—C4—C5 | −144.56 (17) |
C2—C3—C4—C8 | 94.47 (17) | C7—C3—C4—C8 | −20.67 (15) |
C2—C3—C7—C8 | −92.65 (17) | C9—O1—C2—C1 | −138.95 (17) |
C2—C3—C7—Cl1 | 152.67 (14) | C9—O1—C2—C3 | 98.66 (19) |
C2—O1—C9—C10 | 173.39 (18) | C11—O3—C1—C2 | 149.13 (15) |
C2—O1—C9—O2 | −8.5 (3) | C11—O3—C1—C6 | −92.29 (18) |
C3—C2—C1—C6 | −64.25 (18) | C13—O5—C5—C4 | −86.5 (2) |
C3—C2—C1—O3 | 56.56 (18) | C13—O5—C5—C6 | 151.07 (17) |
C3—C4—C8—C7 | 20.85 (14) | C15—O7—C6—C1 | 73.77 (18) |
C3—C4—C8—Cl2 | 146.18 (16) | C15—O7—C6—C5 | −160.03 (15) |
C3—C7—C8—C4 | −21.06 (14) | Cl1—C7—C8—C4 | 90.79 (16) |
C3—C7—C8—Cl2 | −143.59 (16) | Cl1—C7—C8—Cl2 | −31.7 (2) |
C4—C3—C7—C8 | 20.60 (14) | O1—C2—C1—C6 | 173.79 (13) |
C4—C3—C7—Cl1 | −94.08 (15) | O1—C2—C1—O3 | −65.40 (16) |
C4—C5—C6—C1 | −43.8 (2) | O1—C2—C3—C4 | 166.70 (14) |
C4—C5—C6—O7 | −168.35 (14) | O1—C2—C3—C7 | −95.55 (19) |
C5—C4—C8—C7 | 145.72 (17) | O5—C5—C4—C3 | −93.81 (18) |
C5—C4—C8—Cl2 | −89.0 (2) | O5—C5—C4—C8 | 159.49 (15) |
C5—C6—C1—C2 | 63.27 (18) | O5—C5—C6—C1 | 77.40 (18) |
C5—C6—C1—O3 | −55.66 (19) | O5—C5—C6—O7 | −47.11 (18) |
C5—O5—C13—C14 | 179.9 (2) | O7—C6—C1—C2 | −174.09 (13) |
C5—O5—C13—O6 | 2.2 (3) | O7—C6—C1—O3 | 66.98 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O4 | 0.95 (3) | 2.35 (2) | 2.690 (3) | 100.5 (17) |
C1—H1···O8 | 0.95 (3) | 2.52 (2) | 3.031 (3) | 114.1 (17) |
C2—H2···O2 | 1.00 (2) | 2.29 (3) | 2.672 (3) | 100.9 (18) |
C2—H2···O8i | 1.00 (2) | 2.31 (2) | 3.279 (2) | 161 (2) |
C8—H8···O8i | 0.89 (3) | 2.50 (3) | 3.339 (3) | 158 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H20Cl2O8 |
Mr | 411.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 8.9489 (5), 11.0230 (8), 11.2885 (7) |
α, β, γ (°) | 111.427 (2), 98.281 (1), 108.834 (1) |
V (Å3) | 936.70 (10) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.39 |
Crystal size (mm) | 0.32 × 0.21 × 0.20 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID S diffractometer |
Absorption correction | Multi-scan (Blessing, 1995) |
Tmin, Tmax | 0.909, 0.926 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 64683, 7145, 6532 |
Rint | 0.045 |
(sin θ/λ)max (Å−1) | 0.771 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.076, 0.190, 1.32 |
No. of reflections | 7145 |
No. of parameters | 271 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.26 |
Computer programs: CrystalClear (Rigaku, 2005), CrystalClear, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
C2—C1 | 1.514 (3) | C7—C8 | 1.538 (3) |
C2—C3 | 1.520 (3) | C15—C16 | 1.485 (3) |
C3—C4 | 1.567 (3) | Cl1—C7 | 1.788 (2) |
C3—C7 | 1.552 (3) | Cl2—C8 | 1.769 (2) |
C4—C8 | 1.534 (3) | O3—C1 | 1.447 (2) |
C5—C4 | 1.522 (3) | O4—C11 | 1.199 (3) |
C5—C6 | 1.526 (2) | O5—C13 | 1.348 (2) |
C6—C1 | 1.525 (2) | O7—C15 | 1.354 (2) |
C4—C5—C6 | 111.59 (14) | O3—C1—C2 | 108.45 (14) |
C4—C8—C7 | 89.45 (16) | O5—C5—C6 | 109.17 (15) |
C5—C4—C3 | 121.16 (15) | O6—C13—C14 | 125.2 (2) |
C8—C4—C3 | 87.36 (14) | O6—C13—O5 | 123.1 (2) |
O1—C2—C1 | 107.03 (14) | O7—C6—C5 | 107.94 (13) |
C1—C2—C3—C7 | 144.89 (17) | C4—C5—C6—O7 | −168.35 (14) |
C2—C3—C4—C5 | −29.4 (2) | C5—C4—C8—C7 | 145.72 (17) |
C2—C3—C4—C8 | 94.47 (17) | C5—O5—C13—C14 | 179.9 (2) |
C3—C4—C8—C7 | 20.85 (14) | C6—C5—C4—C3 | 27.2 (2) |
C3—C7—C8—C4 | −21.06 (14) | C7—C3—C4—C5 | −144.56 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···O8i | 1.00 (2) | 2.31 (2) | 3.279 (2) | 161 (2) |
C8—H8···O8i | 0.89 (3) | 2.50 (3) | 3.339 (3) | 158 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Carbohydrates are densely functionalized molecules and, as a result, their synthesis often requires many reaction steps, usually including the manipulation of different protecting groups. There are many synthetic strategies leading to the various conduritol isomers and their derivatives (Gültekin et al., 2004). We have previously used a photo-oxygenation reaction to introduce two oxygen functionalities in the 1,4-positions of the appropriate dienes, followed by cleavage of the peroxide linkage (Sütbeyaz et al., 1990; Seçen et al., 1990, 1992, 1993; Salamci et al., 1997; Kara & Balci, 2003). cis-Dichlorobicyclooctadiene, (1), was synthesized as described in the literature (Gözel et al., 1991). Photooxidation of (1) with singlet oxygen gave the expected endoperoxide, (2) (see scheme) (Reppe et al., 1948). Reduction of the peroxide bond in (2) was performed with thiourea under very mild conditions to give the diol, (3a) (Kelebekli et al., 2005; Balci, 1981). For further proof of the structure, (3a) was converted into the corresponding diacetate, (3 b), which was fully characterized by spectroscopic methods. cis-Hydroxylation of (3b) with KMnO4 at 263 K gave a mixture of diols (4a) and (5a) in a ratio of 1:1. These were converted into the tetraacetate derivatives, (4b) and (5b), which were separated by fractional crystallization from hexane–CH2Cl2. The title compound, isomer (4b), crystallized out first (Kelebekli et al., 2005). The exact configuration of compound (4b) has now been determined by X-ray diffraction analysis. The structure provides information on the stereochemical course of the chlorination, photo-oxidation and hydroxylation of the reaction.
Compound (4b) crystallizes in space group P1, with Z = 2. It contains a central non-planar cyclohexane ring with a cyclobutane fused to it. Each C atom is tetrahedral. The all-cis stereochemistry of the four acetate groups was determined unequivocally. The same cis stereochemistry was also seen in the dibromotetraacetate compound (Kara et al., 1994), but there the Br atoms had a trans conformation.
All the substituents, including the acetoxy and chloro groups, are on the same side of the bicycle (syn conformation). In addition to this, the Cl atoms have cis stereochemistry. The six-membered ring adopts a chair conformation, with puckering parameters (Cremer & Pople, 1975) QT = 0.525 (2) Å, θ = 151.1 (2)° and ϕ = 185.7 (5)° (Fig. 1).
The cyclobutane moiety is appreciably distorted, with C—C distances in the range 1.534 (3)–1.567 (3) Å. The strong electronegativity of the Cl atoms along the C3—C7—Cl1 and C4—C8—Cl2 chains causes elongation of the C3—C4 bond.
Intermolecular C—H···O hydrogen bonds between cyclohexane H atoms of the cyclic system and the acetyl O atom are effective in determining the molecular conformation of (4b) [C2···O8i = 3.279 (2) Å and C8···O8i = 3.339 (3) Å; symmetry code: (i) 1 − x, 1 − y, 1 − z]. The molecules are elongated approximately parallel to the (001) plane and are stacked approximately along the a direction (Fig.2).