Heterocyclic aromatic amide protecting groups for aryl and phthalocyaninesulfonic acids

Abstract

Pyroles, indole, imidazole, and a pyrazole were treated with 3,4-dibromobenzenesulfonyl chloride to form 3,4-dibromobenzenesulfonamides. The l-(3,4-dibromophenylsulfonyl)pyrrole and I -(3,4-dibromophenylsullonyl)indole were stable to CUCN iu DMF to produce l{3,4-dioyanophenylsulfonyl)pynole and l-(3.4-dicyanophenylsulfbnyl)indole, which upon treatment rvith ammonia in 2-N,,V-dimethylaminoethanol gave the protected phthalocyanine-2,9,16,23-tetrasulfonamides. Base cleavage of these sulfonamides yielded the free acids. A mixed conclensation of 4,5-diheptylphthalonitrile and 1-(3,4-dicyanophenylsulfonyl)pynole gave 9,10,16.17,23,24-hexakis(1-heptyl)-2-(lpyrrolylsulfonyl)phthalocyanine. Cleavage of the latter yielded the lithium salt of the monosulfonic acid.Ke"v words: sulfonic acid blocking groups, phthalocyanine sulfonic acids, l-(3,4-dicyanophenylsulfonyl)pynole, I -(3,4-dicyanophenyl sulfonyl)indole. 2). Although phthalocyanine -2,9,1 6,23 -tetr asulfonic acid is commercially available as a mixtufe of isomers, it has been shown that phthalocyanine-2-sulfonic acid ard plrthalocyanine-2,9-disulfonic acid are more effective for direct cell kill (3)(4)(5)(6)(7)(8)(9)

Synthesis and Radiopharmacological Characterisation of a Fluorine‐18‐Labelled Azadipeptide Nitrile as a Potential PET Tracer for in vivo Imaging of Cysteine Cathepsins

“…Compound 2 (0.83 g (77 % purity), 5.03 mmol) was added. : [53] Ethylene glycol-1,2-bis(3,4-dibromobenzenesulfonate) (5 c): Potassium trimethylsilanolate (1.92 g, 14.96 mmol) was added as a solid in portions to a solution of ethylene glycol (0.19 g, 2.99 mmol) and 4 (2.5 g, 7.48 mmol) in THF (6 mL) under ice cooling. The combined organic layers were washed with H 2 O (30 mL) and brine (30 mL), then dried over Na 2 SO 4 .…”

“…The solvent was removed in vacuo and the remaining residue was purified by vacuum distillation (0.038 mbar, 120 8C) to obtain 4 (2.96 g, 77 %) as a yellowish waxy solid; mp: 38-40 8C (lit. : [53] Ethylene glycol-1,2-bis(3,4-dibromobenzenesulfonate) (5 c): Potassium trimethylsilanolate (1.92 g, 14.96 mmol) was added as a solid in portions to a solution of ethylene glycol (0.19 g, 2.99 mmol) and 4 (2.5 g, 7.48 mmol) in THF (6 mL) under ice cooling. The reaction mixture was stirred for 2 h in the ice bath and subsequently diluted with ice-cold H 2 O (30 mL) and CH 2 Cl 2 (20 mL).…”

Isomeric separation and identification of tetra-, tri-, and di-β-sulphonic phthalocyanine zinc complexes

“…Using such starting material will still produce mix PCs with sulphonic groups on either α-or β-positions [25]. Using pure 4-sulphonic fragments can ensure the sulphonic groups on β-positions [10,26,27]. However, isomers still existed due to the different arrangement patterns of substituents on the PC macrocycle.…”

Synthesis of organo-soluble metallophthalocyanines bearing electron-withdrawing substituents

“…Leznoff et al reported zinc sulfonamidophthalocyanines with N-heterocyclic aromatic protecting groups for sulfonic acids in the view of their potential as photodynamic therapy agents against cancer tumors [29]. A sulfonamide linkage was also used for the covalent attachment of metallophthalocyanines to a silica support [14,30,31] and very recently we have reported the synthesis of metallophthalocyanines linked to organic copolymers and their high efficiency as supported oxidative catalysts [32].…”