Syntheses and Reactions of 2,5‐Disulfobenzene‐1‐diazonium Salts: Towards Functionalized Sulfonate Metal–Organic Frameworks

Abstract

Keywords: Sulfur / Copper / Cross-coupling / Barium / Metal-organic frameworks A preparation, separation, and purification protocol for 2-substituted 1,4-benzenedisulfonic acids by exploiting crystallization of the barium salts and their subsequent protonation with cation-exchange resin was developed. This technique was applied to the preparation of 2-chloro-, 2-bromo-, 2-iodo-, and 2-hydroxy-1,4-benzenedisulfonic acids. The iodo derivative was submitted to Suzuki coupling reac-

Crystal structure of di-acetato-bis-pyridine-palladium(II), [Pd(C2H3O2)2(C5H5N)2], C14H16N2O4Pd

“…For several years we explored the potential of sulfonic acids for the construction of frameworks (MOFs) and coordination polymers [4][5][6][7][8][9][10]. In the course of introducing catalytically active metal atoms such as palladium in the desired coordination complexes the usage of Pd(OAc) 2 as the starting material resulted in the here presented compound, which has been prepared and characterized up to now only via IR and elemental analysis but without structure elucidation [11].…”

Synthesis of Aromatic and Aliphatic Di-, Tri-, and Tetrasulfonic Acids

“…The diazonium salt can be further transformed, e.g., by reduction or Sandmeyer reaction (Scheme 11). 30 For example, compound 2 (X = H) could be obtained from the diazonium salt by reduction with EtOH at 100 °C, the yield is, however, low (Table 1, entry 1), thus, this protocol cannot compete with the method described in Scheme 3 (84% yield of compound 2 over three steps). The challenge associated with the procedure shown in Scheme 11 is actually the purification and isolation of the products 2 and 51-54, which is achieved by twofold treatment of the reaction mixture with aqueous BaCl 2 .…”