PAPER
Linear Aromatic Disulfonic Acids as New Linker Molecules
2779
Tolane-4,4¢-disulfonic Acid Dihydrate (8)
CHCl3 (8 mL) to yield the title compound 19 (126 mg, 0.32 mmol,
55%) as a yellow solid; mp 199–201 °C (dec.).
A suspension of dichloride 17 (94 mg, 0.25 mmol) in H2O (10 mL)
was heated to reflux for 18 h. Then THF (5 mL) was added to the
mixture and it was heated to reflux for further 5 h. Subsequently, it
was filtered through a pad of cotton (rinsed with H2O) and the fil-
trate was evaporated in high vacuum to yield the title compound 8
(96 mg, 0.25 mmol, quant) as a light-grey solid; mp 158–160 °C
(DTA/TG).
IR (ATR): 3094 (w), 1712 (br, m), 1583 (m), 1484 (w), 1374 (s),
1328 (m), 1282 (w), 1185 (m), 1166 (s), 1075 (m), 1012 (m), 962
(m), 831 (s), 798 (m), 783 (m), 736 (w), 711 (w), 651 (w), 618 (s)
cm–1.
1H NMR (500 MHz, CDCl3): d = 7.76 (d, J = 5.1 Hz, 4 H), 8.04 (d,
J = 5.1 Hz, 4 H).
13C{1H} NMR (500 MHz, CDCl3): d = 77.9 (C), 81.2 (C), 127.1 (2
CH), 128.5 (C), 133.6 (2 CH), 144.3 (C).
HRMS (EI, 70 eV): m/z calcd for C16H8Cl2O4S2 [M+]: 397.9241;
found: 397.9233.
IR (ATR): 2704 (br, m), 1666 (br, m), 1596 (m), 1499 (w), 1395
(w), 1114 (br, s), 1101 (s), 996 (br, s), 829 (s), 685 (s) cm–1.
1H NMR (500 MHz, D2O): d = 7.60 (d, J = 8.4 Hz, 4 H), 7.72 (d,
J = 8.4 Hz, 4 H).
13C{1H} NMR (500 MHz, D2O): d = 90.3 (C), 125.3 (C), 125.8 (2
CH), 132.2 (2 CH), 142.6 (C).
Anal. Calcd for C16H8Cl2O4S2 (399.27): C, 48.13; H, 2.02; S, 16.06.
Found: C, 47.75; H, 1.83; S, 16.36.
MS (ESI, neg. mode): m/z = 337 [M – H+], 168 [M – 2 H+].
HRMS (ESI, neg. mode): m/z calcd for C14H8O6S2 [M – 2 H+]:
1,4-Bis(4-sulfophenyl)butadiyne Dihydrate (10)
2–
167.9887; found: 167.9890.
A suspension of acid chloride 19 (40 mg, 0.10 mmol) in H2O (10
mL) was heated to reflux for 22 h. Subsequently, THF (6 mL) was
added and the mixture was heated to reflux for further 6 h. After fil-
tration, all volatile materials were removed in high vacuum to yield
the title compound 10 (33 mg, 0.083 mmol, 83%) as a light-grey
solid; mp 174–176 °C (DTA/TG).
1,4-Bis[4-(acetylthio)phenyl]butadiyne (18)
CuI (28.6 mg, 0.15 mmol, 0.05 equiv) and NiCl2·6 H2O (35.7 mg,
0.15 mmol, 0.05 equiv) were added to a solution of TMEDA (70
mg, 0.60 mmol, 0.20 equiv) in THF (12 mL). After stirring the re-
sulting suspension for 2 min at 23 °C, alkyne 15 (529 mg, 3.00
mmol, 1 equiv) and THF (2 mL) were added and the resulting mix-
ture was stirred for 60 h at 23 °C in an atmosphere of air (a reflux
condenser was used in order prevent evaporation of the solvent),
while following the conversion by GLC. After dilution with H2O
(50 mL) and CH2Cl2 (80 mL), the layers were separated and the
aqueous layer was extracted with CH2Cl2 (2 × 80 mL). The com-
bined organic layers were washed with H2O (80 mL), dried
(MgSO4), and the solvent was evaporated after filtration. Chroma-
tography on SiO2 (gradient elution from hexane–MTBE, 10:1 via
2:1 to hexane–CH2Cl2, 2:1 to neat CH2Cl2) furnished title com-
pound 18 (344 mg, 0.98 mmol, 65%) as a yellow solid; mp 279–
280 °C; Rf = 0.14 (hexane–MTBE, 10:1).
IR (ATR): 2848 (br, m) 1668 (br, m), 1590 (m), 1557 (w), 1486 (w),
1396 (w), 1356 (m), 1160 (s), 1117 (br, s), 1061 (s), 1030 (s), 1001
(br, s), 894 (br, s), 831 (s), 786 (m), 646 (br, s) cm–1.
1H NMR (500 MHz, D2O): d = 7.14 (d, J = 7.3 Hz, 4 H), 7.39 (d,
J = 7.3 Hz, 4 H).
13C{1H} NMR (500 MHz, D2O): d = 75.8 (C), 81.8 (C), 124.2 (C),
125.7 (2 CH), 133.2 (2 CH), 143.1 (C).
–
HRMS (ESI, neg. mode): m/z calcd for C16H9O6S2 [M – H+]:
360.9846; found: 360.9850.
Acknowledgment
IR (ATR): 3365 (w), 2922 (w), 1900 (w), 1696 (s), 1586 (w), 1480
(m), 1394 (m), 1353 (m), 1267 (w), 1114 (s), 1088 (s), 1012 (m),
9584 (s), 820 (s), 627 (s) cm–1.
We thank Dr. Herbert Frey for his support and Christina Zitzer for
DTA measurements.
1H NMR (500 MHz, CDCl3): d = 2.44 (s, 6 H), 7.39 (d, J = 8.2 Hz,
4 H), 7.55 (d, J = 8.2 Hz, 4 H).
13C{1H} NMR (500 MHz, CDCl3): d = 30.3 (CH3), 75.3 (C), 81.4
(C), 122.7 (C), 129.5 (C), 133.0 (2 CH), 134.2 (2 CH), 193.0 (C).
HRMS (EI, 70 eV): m/z calcd for C20H14O2S2 [M+]: 350.0435;
found: 350.0444.
References
(1) (a) Eberle, U.; Felderhoff, M.; Schüth, F. Angew. Chem. Int.
Ed. 2009, 48, 6608; Angew. Chem. 2009, 121, 6732.
(b) Seayad, A. M.; Antonelli, D. M. Adv. Mater. 2004, 16,
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(2) (a) McKinlay, A. C.; Morris, R. E.; Horcajada, P.; Ferey, G.;
Gref, R.; Couvreur, P.; Serre, C. Angew. Chem. Int. Ed.
2010, 49, 6260; Angew. Chem. 2010, 122, 6400. (b) Ma, S.;
Zhou, H.-C. Chem. Commun. 2010, 46, 44. (c) Wang, Z.;
Cohen, S. M. Chem. Soc. Rev. 2009, 38, 1315.
Anal. Calcd for C20H14O2S2 (350.45): C, 68.54; H, 4.03; S, 18.30.
Found: C, 68.53; H, 4.11; S, 18.20.
1,4-Bis[4-(chlorosulfonyl)phenyl]butadiyne (19)
NCS (609 mg, 4.56 mmol, 8 equiv) and aq HCl (2 mol/L, 0.63 mL,
1.26 mmol, 2.2 equiv) were added at 0 °C to a suspension of diyne
18 (200 mg, 0.57 mmol, 1 equiv) in MeCN (1.6 mL) and the result-
ing mixture was stirred for 3 h at 10–15 °C. More of the above HCl
(0.20–0.50 mL) was added. If no change of the mixture (clearing)
appeared, the reaction temperature was brought to 23 °C and then
stirred for further 90 min. Otherwise, the mixture was left for further
30 min at 10–15 °C before stirring for 90 min at 23 °C. After dilu-
tion with CH2Cl2 (20 mL) and H2O (20 mL), the layers were sepa-
rated and the aqueous phase extracted with CH2Cl2 (2 × 20 mL).
The combined organic layers were washed with H2O (40 mL), dried
(MgSO4), and evaporated after filtration. The residue was chro-
matographed (SiO2, CH2Cl2, Rf = 0.75) to yield a crude material
(241 mg), which was further purified by recrystallization from
(d) Farrusseng, D.; Aguado, S.; Pinel, C. Angew. Chem. Int.
Ed. 2009, 48, 7502; Angew. Chem. 2009, 121, 7638.
(e) Fischer, R. A.; Wöll, C. Angew. Chem. Int. Ed. 2008, 47,
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Schubert, M.; Teich, F.; Puetter, H.; Schierle-Arndt, K.;
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Synthesis 2011, No. 17, 2775–2780 © Thieme Stuttgart · New York