FULL PAPER
1639 (w), 1453 (w), 1222 (m), 1162 (s), 1062 (m), 1040 (m), 987 (–)-(R,R)-1,2-Cyclohexanedisulfonic Acid Dihydrate [(–)-3]: This
(w), 823 (w), 776 (m), 767 (m), 647 (m), 625 (m), 554 (m), 540 (m)
cm–1. C6H10BaO6S2 (379.59): calcd. C 18.99, H 2.66, S 16.89; found
C 18.92, H 2.69, S 16.87.
compound was obtained in analogy to its enantiomer (+)-3 using
(–)-8 (80 mg, 223 μmol) as starting material. The product (–)-3
(62 mg, 221 μmol, 99%) could be obtained as a strongly hygro-
scopic, colorless solid. [α]2D0 = –43 (c = 1 gL–1 in H2O).
(؎)-trans-1,2-Cyclohexanedisulfonic Acid Monosodium Salt Di-
hydrate [(؎)-7]: Barium salt (Ϯ)-6 (75 mg, 198 μmol) was sus-
pended in water (5 mL) and transferred on top of a column (20 g,
Amberlyst 15). The corresponding acid was eluted with water until
the pH of the eluent was neutral (ca. 30 mL). The resulting solution
was concentrated under vacuum, redissolved in water (5 mL), and
treated with NaHCO3 (32 mg, 386 μmol). Slow evaporation of the
solvent at ambient temperature yielded the title compound (Ϯ)-7
as colorless crystals (59 mg, 194 μmol, 98%) suitable for X-ray
analysis. C6H15NaO8S2 (302.29): calcd. C 23.84, H 5.00, S 21.21;
found C 24.01, H 4.98, S 20.96.
(–)-Disodium (R,R)-1,2-Cyclohexanedisulfonate·1.8H2O [(–)-9]:
NaHCO3 (37 mg, 435 μmol) was added to a solution of sulfonic
acid (–)-(R,R)-3 (62 mg, 223 μmol) in water (5 mL). Colorless crys-
tals (71 mg, 221 μmol, 99%) suitable for X-ray analysis could be
obtained by slow evaporation of the solvent at ambient tempera-
ture. [α]2D0 = –22 (c = 1 gL–1 in H2O).
(Dimethylammonium) Silver(I) (R,R)-1,2-Cyclohexanedisulfonate
[(R,R)-10]: A glass ampoule was filled with Ag2CO3 (44 mg,
0.16 mmol), (–)-(R,R)-3 (30 mg, 0.11 mmol), and DMF (2.5 mL)
and it was torch-sealed under vacuum. The ampoule was placed in
a resistance furnace and heated up to 105 °C within 6 h. After 24 h
the furnace was slowly cooled to room temperature within 96 h.
The product was obtained as transparent single crystals in approxi-
mately 60% yield with respect to the initial Ag2CO3. They were
separated from the supernatant by decantation.
(R,R)-1,2-Cyclohexanediammonium (S,S)-1,2-Cyclohexanedisulfon-
ate [(+)-8] and Its Enantiomer (–)-8: Barium salt (Ϯ)-6 (1.80 g,
4.74 mmol) was suspended in water (50 mL) and transferred on top
of a column (20 g, Amberlyst 15). The corresponding acid was
eluted with water until the pH of the eluent was neutral (ca.
150 mL). The resulting solution was treated with (R,R)-1,2-diami-
nocyclohexane (217 mg, 1.90 mmol) and the solvent was evapo-
rated under reduced pressure. The crude product was recrystallized
from methanol (100 mL) until the solid showed a constant optical
rotation (three times are sufficient). Enantiomerically pure product
(+)-8 (540 mg, 1.51 mmol, 79%) could be obtained as a colorless
solid (decomp. 250 °C). [α]2D0 = +18 (c = 1 gL–1 in H2O). The super-
natants of the above crystallizations were combined, (S,S)-1,2-di-
aminocyclohexane (217 mg, 1.90 mmol) was added, and the re-
sulting mixture evaporated. The residue was recrystallized twice
from methanol (100 mL) to yield enantiomerically pure (–)-8
(456 mg, 1.27 mmol, 67%) as a colorless solid (decomp. 250 °C).
Supporting Information (see footnote on the first page of this arti-
1
cle): H and 13C{1H} NMR spectra of all products.
Acknowledgments
The authors are grateful to Dr. Marc Schmidtmann for X-ray
crystallography. This work was generously supported by the
Deutsche Forschungsgemeinschaft (DFG).
[1] a) J. Gascon, A. Corma, F. Kapteijn, F. X. Llabres i Xamena,
ACS Catal. 2014, 4, 361–378; b) A. Dhakshinamoorthy, M.
Opanasenko, J. Cejka, H. Garcia, Catal. Sci. Technol. 2013, 3,
2509–2540.
[2] S.-L. Li, Q. Xu, Energy Environ. Sci. 2013, 6, 1656–1683.
[3] Z. R. Herm, E. D. Bloch, J. R. Long, Chem. Mater. 2014, 26,
323–338.
1
[α]2D0 = –15 (c = 1 gL–1 in H2O). H NMR (500 MHz, D2O): δ =
3.65 (d, J = 4.9 Hz, 2 H), 3.57–3.35 (m, 2 H), 2.32–2.23 (m, 4 H),
2.23–2.11 (m, 2 H), 1.99–1.89 (m, 2 H), 1.86–1.75 (m, 2 H), 1.71–
1.58 (m, 4 H), 1.53–1.41 (m, 2 H) ppm. 13C{1H} NMR (126 MHz,
D2O): δ = 55.18 (CH), 52.28 (CH), 29.33 (CH2), 22.81 (CH2), 22.11
(CH ), 19.68 (CH ) ppm. IR (ATR): ν = 3375 (br), 2923 (m), 2759
˜
2
2
[4] M. Yoon, K. Suh, S. Natarajan, K. Kim, Angew. Chem. Int.
Ed. 2013, 52, 2688–2700; Angew. Chem. 2013, 125, 2752–2764.
[5] a) H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi,
Science 2013, 341, 1230444; b) T. R. Cook, Y.-R. Zheng, P. J.
Stang, Chem. Rev. 2013, 113, 734–777; c) Y.-R. Lee, J. Kim,
W.-S. Ahn, Korean J. Chem. Eng. 2013, 30, 1667–1680; d) C.
Wang, D. Liu, W. Lin, J. Am. Chem. Soc. 2013, 135, 13222–
13234.
(m), 2208 (w), 1584 (w), 1519 (w), 1455 (w), 1404 (w), 1208 (s),
1171 (vs), 1053 (s), 1034 (vs), 986 (m), 911 (w), 879 (w), 825 (w),
762 (m), 731 (w), 628 (m), 613 (s), 542 (s) cm–1. C12H26N2O6S2
(358.47): calcd. C 40.21, H 7.31, N 7.81, S 17.89; found C 40.21,
H 7.56, N 7.52, S 18.11. Single crystals of compound (+)-8 suitable
for X-ray analysis were obtained by slow evaporation of a solution
in water.
[6] a) A. Mietrach, T. W. T. Muesmann, J. Christoffers, M. S.
Wickleder, Eur. J. Inorg. Chem. 2009, 5328–5334; b) T. W. T.
Muesmann, C. Zitzer, A. Mietrach, T. Klüner, J. Christoffers,
M. S. Wickleder, Dalton Trans. 2011, 40, 3128–3141; c) T. W. T.
Muesmann, A. Mietrach, J. Christoffers, M. S. Wickleder, Z.
Anorg. Allg. Chem. 2010, 636, 1307–1312.
[7] T. W. T. Muesmann, C. Zitzer, M. S. Wickleder, J. Christoffers,
Inorg. Chim. Acta 2011, 369, 45–48.
[8] T. W. T. Muesmann, M. S. Wickleder, C. Zitzer, J. Christoffers,
Synlett 2013, 24, 959–962.
[9] a) I. F. Hernandez-Ahuactzi, H. Höpfl, V. Barba, P. Roman-
Bravo, L. S. Zamudio-Rivera, H. I. Beltran, Eur. J. Inorg.
Chem. 2008, 2746–2755; b) Y.-Z. Zheng, W. Xue, M.-L. Tong,
X.-M. Chen, S.-L. Zheng, Inorg. Chem. 2008, 47, 11202–11211;
c) S.-S. Chen, Y. Zhao, J. Fan, T.-a. Okamura, Z.-S. Bai, Z.-H.
Chen, W.-Y. Sun, CrystEngComm 2012, 14, 3564–3576; d) Y.-
C. Ou, D.-S. Zhi, W.-T. Liu, Z.-P. Ni, M.-L. Tong, Chem. Eur.
J. 2012, 18, 7357–7361; e) E. Y. Kim, H. M. Park, H.-Y. Kim,
J. H. Kim, M. Y. Hyun, J. H. Lee, C. Kim, S.-J. Kim, Y. Kim,
J. Mol. Struct. 2011, 994, 335–342; f) I. H. Kim, X. Wang, A. J.
(+)-(S,S)-1,2-Cyclohexanedisulfonic Acid Dihydrate [(+)-3]: Com-
pound (+)-8 (387 mg, 1.08 mmol) was dissolved in water (20 mL)
and transferred on top of a column (20 g, Amberlyst 15). The acid
was eluted with water until the pH of the eluent was neutral (ca.
80 mL). After removal of the water by rotary evaporation and dry-
ing of the residue under high vacuum, the title compound (+)-3
(303 mg, 1.08 mmol, 100%) was obtained as a strongly hygro-
scopic, colorless solid. [α]2D0 = +37 (c = 1 gL–1 in H2O). H NMR
1
(500 MHz, D2O): δ = 3.56 (br. d , J = 5.8 Hz, 2 H), 2.17 (br. d, J
= 14.5 Hz, 2 H), 2.12–2.01 (m, 2 H), 1.77–1.64 (m, 2 H), 1.58–1.50
(m, 2 H) ppm. 13C{1H} NMR (126 MHz, D2O): δ = 55.08 (CH),
21.99 (CH ), 19.59 (CH ) ppm. IR (ATR): ν = 2953 (m), 2928 (m),
˜
2
2
2876 (m), 2441 (br), 2166 (br), 1780 (br), 1453 (w), 1312 (w), 1290
(w), 1260 (w), 1160 (m), 1084 (s), 1030 (s), 994 (s), 913 (m), 854
(m), 810 (m), 732 (m), 682 (m), 644 (w), 589 (m) cm–1. MS (ESI,
pos.): m/z = 245 [M + H+], 277 [M + Na+]. C6H12O6S2·2H2O
(280.31): calcd. C 25.71, H 5.75, S 22.88; found C 25.49, H 5.74, S
22.77.
Eur. J. Inorg. Chem. 2014, 6225–6231
6230
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim