Octahydropentalene 2,5-Disulfonic Acid – A New Linker Molecule for Coordination Polymers

Dedicated to Professor Jürgen Martens on the occasion of his 65^th birthday.

Abstract

Octahydropentalene 2,5-disulfonic acid was prepared in five steps as a single stereoisomer from the corresponding bicyclic diketone. The latter was first reduced followed by activation of the secondary-alcohol functions and nucleophilic substitution with thioacetate. The thioester moieties were oxidatively degraded to the bischlorosulfonyl derivative. On this stage the configuration was established by a X-ray single-crystal analysis. Hydrolysis gave the target compound as the trihydrate.

Keywords

bicyclic compounds - carbocycles - diols - sulfur - thiols

• References and Notes

• 1 New address: Ferdinand Eimermacher GmbH & Co. KG, Westring 24, 48356 Nordwalde, Germany.

Reviews:
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• 8 Octahydropentalene-2,5-diol (2) NaBH₄ (1.86 g, 49.3 mmol) was added to a solution of diketone 1 (2.73 g, 19.7 mmol) in MeOH (33 mL), while cooling the reaction mixture with an ice-water bath. After stirring the mixture for further 2 h at ambient temperature, it was first diluted (upon cooling with an ice-water bath) with hydrochloric acid (62 mL, 2 mol/L), then with aq NaOH solution (155 mL, 4 mol/L) and finally extracted with MTBE (3 × 140 mL). The combined organic layers were dried (MgSO₄) and evaporated after filtration. The residue was recrystallized from MTBE (ca. 70 mL) to give the title compound (1.92 g, 13.5 mmol, 69%) as a colorless solid (mp 72–73 °C), which consisted of two diastereoisomers (endo,endo/endo,exo = 5:1 by GLC). Alternatively, the crude product could be purified by chromatography [SiO₂, MTBE → acetone; R_f = 0.26 (MTBE)], then yielding a mixture with a dr of 3.5:1 (by GLC). ¹H NMR (500 MHz, CDCl₃): δ (major isomer) = 1.69–1.78 (m, 4 H), 2.06–2.12 (m, 4 H), 2.51–2.53 (m, 2 H), 3.92 (br s, 2 H), 4.23–4.26 (m, 2 H) ppm; δ (minor isomer) = 1.27–1.29 (m, 4 H), 1.78–1.79 (m, 4 H), 2.53–2.56 (m, 2 H), 4.16–4.17 (m, 1 H), 4.43–4.44 (m, 1 H) ppm. ¹³C{¹H} NMR (125 MHz, CDCl₃): δ (major isomer) = 41.15 (CH), 43.41 (CH₂), 76.19 (CH) ppm; δ (minor isomer) = 38.84 (CH), 42.35 (CH₂) 42.58 (CH₂), 74.68 (CH), 75.14 (CH) ppm. IR (ATR): 3263 (br, s), 2943 (s), 2903 (m), 2870 (br, m), 1465 (m), 1439 (m), 1344 (s), 1303 (m), 1256 (m), 1192 (m), 1105 (s), 1072 (s), 1032 (s), 983 (s), 777 (m), 694 (br, m) cm^–1. HRMS (ESI, +): m/z calcd for C₈H₁₄LiO₂: 149.1154; found: 149.1154 [M + Li⁺]; C₈H₁₄O₂ (142.20).
• 9 Camps P, Lukach AE, Vazquez S. Tetrahedron 2001; 57: 2419
• 10 Octahydropentalene-2,5-diylbis(4-toluenesulfonate) (3) 4-MeC₆H₄SO₂Cl (15.4 g, 80.7 mmol) was added to an ice-cooled suspension of Et₃N (11.3 mL, 80.7 mmol) and diol 2 (2.30 g, 16.1 mmol, dr = 5:1) in CH₂Cl₂ (40 mL). After stirring for 24 h at ambient temperature, the mixture was diluted with H₂O (60 mL) and MTBE (60 mL). The layers were separated, and the aqueous phase was diluted with brine (50 mL) and extracted twice with MTBE (each 50 mL). The combined organic layers were washed with brine (50 mL), dried (MgSO₄), and evaporated after filtration. Chromatography of the residue [SiO₂, hexane–MTBE = 5:1 → 1:1 → MTBE, R_f = 0.72 (MTBE)] gave the title compound (5.77 g, 12.8 mmol, 80%) as a light yellow oil, which consisted of two diastereoisomers (endo,endo/endo,exo = 6:1 by NMR). ¹H NMR (500 MHz, CDCl₃): δ = 1.68–1.71 (m, 4 H), 1.98–2.00 (m, 4 H), 2.28–2.33 (m, 2 H), 2.44 (s, 6 H), 4.78–4.80 (m, 2 H), 7.32 (d, J = 8.0 Hz, 4 H), 7.75 (d, J = 8.0 Hz, 4 H) ppm; signals of the minor isomer were not listed. ¹³C{¹H} NMR (125 MHz, CDCl₃): δ = 14.06 (CH₃), 37.62 (CH), 38.75 (CH₂), 83.97 (CH), 127.60 (2 CH), 129.82 (2 CH), 134.14 (C), 144.55 (C) ppm; signals of the minor isomer were not listed. IR (ATR): 2964 (br, w), 1598 (m), 1352 (s), 1306 (w), 1188 (m), 1171 (s), 1096 (m), 1018 (m), 969 (m), 926 (m), 880 (s), 855 (s), 813 (s) 768 (m), 752 (s), 666 (s) cm^–1. MS (ESI, +): m/z = 473 [M + Na⁺]; C₂₂H₂₆O₆S₂ (450.57).
• 11 exo,exo-2,5-Di(acetylthio)octahydropentalene (4) KSAc (4.81 g, 42.2 mmol) was added to a solution of bistosylate 3 (3.79 g, 8.43 mmol) in MeCN (34 mL), and the resulting mixture was heated to reflux for 3.5 h. Subsequently, it was diluted with MTBE (80 mL) and H₂O (80 mL), and the layers were separated. The aqueous layer was extracted twice with MTBE (2 × 50 mL). The combined organic layers were dried (MgSO₄) and evaporated after filtration. The residue was chromatographed [SiO₂, hexane → hexane–CH₂Cl₂ = 1:1 → CH₂Cl₂ → MTBE; R_f = 0.40 (hexane–CH₂Cl₂ = 1:1)] to furnish the title compound 3 (787 mg, 3.04 mmol, 36%) as a single isomer and as a brown solid, mp 74–76 °C. ¹H NMR (500 MHz, CDCl₃): δ = 1.78 (t, J = 6.5 Hz, 8 H), 2.27 (s, 6 H), 2.66–2.67 (m, 2 H), 3.80 (pent, J = 6.5 Hz, 2 H) ppm. ¹³C{¹H} NMR (125 MHz, CDCl₃): δ = 30.67 (CH), 39.89 (CH₂), 41.09 (CH₃), 43.03 (CH), 196.08 (C) ppm. IR (ATR): 3363 (w), 2976 (w), 2943 (m), 2930 (m), 2855 (m), 1675 (s), 1442 (m), 1421 (m), 1353 (m), 1276 (m), 1261 (m), 1148 (m), 1122 (s), 1104 (s), 1005 (m), 956 (s), 931 (m), 907 (m), 83 5 (m), 646 (m), 624 (s) cm^–1. MS (ESI, +): m/z = 281 [M + Na⁺]. Anal. Calcd for C₁₂H₁₈O₂S₂ (258.40): C, 55.78; H, 7.02. Found C, 55.56; H, 7.01.
• 12 exo,exo-Octahydropentalene-2,5-disulfonic Acid Dichloride (5) While cooling with an ice-water bath, NCS (2.71 g, 20.3 mmol) and hydrochloric acid (2.8 mL, 5.6 mmol, 2 mol/L) were added to a suspension of dithioacetate 4 (656 mg, 2.54 mmol) in MeCN (7.3 mL). The resulting mixture was stirred at 10–15 °C, until a clear solution was formed (ca. 1–1.5 h). It was then stirred at ambient temperature for further 2 h and subsequently diluted with H₂O (40 mL) and CH₂Cl₂ (40 mL). After phase separation, the aqueous layer was extracted twice with CH₂Cl₂ (2 × 40 mL). The combined organic layers were dried (MgSO₄) and evaporated after filtration. The residue was chromatographed [SiO₂, hexane–CH₂Cl₂ = 1:1, R_f = 0.70 (CH₂Cl₂)] to yield a crude material, which was further purified by recrystallization from hexane–CHCl₃ (1:1, 25 mL) to furnish a title compound 5 (615 mg, 2.00 mmol, 79%) as colorless needles, mp 100–101 °C. ¹H NMR (500 MHz, CDCl₃): δ = 2.02 (ddd, J = 15.0, 4.5, 7.5 Hz, 4 H), 2.62 (ddd, J = 15.0, 7.0, 8.5 Hz, 4 H), 3.13–3.18 (m, 2 H), 4.18 (dt, J = 7.0, 7.5 Hz, 2 H) ppm. ¹³C{¹H} NMR (125 MHz, CDCl₃): δ = 35.27 (CH₂), 42.09 (CH), 75.49 (CH) ppm. IR (ATR): 2974 (w), 2942 (w), 2871 (w), 1359 (s), 1331 (m), 1283 (m), 1261 (m), 1149 (s), 1098 (m), 934 (m), 664 (s) cm^–1. MS (CI, NH₃): m/z (%) = 324 (0.5) [M + NH₄ ⁺], 143 (22), 107 (100). Anal Calcd for C₈H₁₂Cl₂O₄S₂ (307.21): C, 31.28; H, 3.94; S, 20.87. Found: C, 31.23; H, 3.75; S, 21.21.
• 13 exo,exo-Octahydropentalene-2,5-disulfonic Acid Trihydrate (6) A suspension of dichloride 5 (220 mg, 0.72 mmol) in H₂O (15 mL) was heated for 5.5 h to reflux. After filtration through Celite, all volatile materials were removed under high vacuum to yield the title compound 6 (209 mg, 0.64 mmol, 90%) as a grey solid, which was determined by DTA/TG to be the trihydrate (mp 185 °C). ¹H NMR (300 MHz, D₂O): δ = 1.58–1.65 (m, 4 H), 1.89–1.99 (m, 4 H), 2.69 (br m, 2 H), 3.30 (tt, J = 7.8, 8.1 Hz, 2 H) ppm. ¹³C{¹H} NMR (125 MHz, D₂O): δ = 35.38 (CH₂), 42.57 (CH), 60.27 (CH) ppm. IR (ATR): 2967 (w), 2873 (w), 1684 (br, m), 1185 (s), 1028 (br, s), 989 (s), 710 (m), 627 (m) cm^–1. HRMS (ESI, –): m/z calcd for C₈H₁₃O₆S₂: 269.0154; found 269.0160 [M – H⁺]; C₈H₁₄O₆S₂·3H₂O (270.32 + 54.05).
• 14 CCDC 914780 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk, or by emailing [e-mail], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: [phone].