N N N M Copyright © 2008 Society of Porphyrins & Phthalocyanines Published on web 11/17/2008 Journal of Porphyrins and Phthalocyanines ICPP-5 paper J. Porphyrins Phthalocyanines 2008; 12: 1090-1095 Published at http://www.u-bourgogne.fr/jpp/ Amphiphilic galactosylated phthalocyanines Ufuk Kumru, Mahmut Ali Ermeydan  , Fabienne Dumoulin  and Vefa Ahsen*  Gebze Institute of Technology, Department of Chemistry, P. O. Box 141, Gebze, 41400 Kocaeli, Turkey Received 26 August 2008 Accepted 23 September 2008 ABSTRACT: Two amphiphilic Ni phthalocyanines bearing a hydrophilic galactose head facing six hydrophobic thiohexyl chains are described. The place of the glycosylation step on the overall syn- thetic pathway is discussed. For the irst time, phthalocyanines are used as acceptors in glycosylation reactions, in excellent yields. Copyright © 2008 Society of Porphyrins & Phthalocyanines. KEYWORDS: galactosylated phthalocyanine, glycosylation acceptor, amphiphilicity. INTRODUCTION Amphiphilic phthalocyanines are expected to ex- hibit self-assembling properties, the studies and ap- plications of which are wide. If a huge number of amphiphilic glycoconjugated molecules are reported [1-2], as either being liquid crystal [3-4] or forming monolayers at the air-water interface [5], only one amphiphilic Pc bearing carbohydrates is reported [6]. In this latter case, its amphiphilic character ari- ses from the nature of the macrocyle, but not from the concomitant presence on a Pc ring of both car- bohydrate hydrophilic and hydrophobic moieties. We present hereafter the synthesis of two galactosylated amphiphilic NiPc: 1 and 2. Their AB3 asymmetric pattern is composed of three dihexylthio hydropho- bic moieties, when a galactose head, grafted onto two different types of spacers, is the hydrophilic part of the structure. Such structures are expected to have in- creased amphiphilic balance. These two spacers have different relative hydrophilicity, one being composed of three methylene, thus quite hydrophobic (Pc 1), while the other one is far more hydrophilic, consis- ting of a tetraethyleneglycol unit (Pc 2) (Chart 1). The grafting of the carbohydrate head was a crucial step of the synthetic pathway. The Pcs bearing carbohy- drate units, reported thus far, are formed from car- bohydrated precursors [6-14], but synthetic conside- rations lead us to use pre-formed hydroxylated Pcs as acceptor in a glycosylation reaction (Scheme 1). The excellent behavior of the two hydroxylated Pcs 7 and 9 as acceptors to be coupled with the trichloroa- cetimidate of 2,3,4,6-tetra-O-benzoylated galactose (the donor) is a promising result to take into account for further design of glycosylated Pcs. EXPERIMENTAL General 4-nitrophthalonitrile [15], monosilylated propane- diol [16], 4-[2-[2-[2-(2-hydroxyethoxy)ethoxy]etho- xy]ethoxy]-1,2-benzenedicarbonitrile (5) [17], dihe- xylthiophthalonitrile (6) [18] and 2,3,4,6-tetra-O-ben- zoyl-α-D-galactopyranosyl trichloroacetimidate 11 [5] have been prepared following the reported procedu- res. Chromatographic puriications were performed on silica gel (Merck, 0.04-0.063 mm) with the indica- ted eluting systems. Infrared spectra were recorded with a Bio-Rad FTS 175C FTIR spectrophotometer. Absorption spectra in the UV-vis region were recor- ded with a Shimadzu 2001 UV Pc spectrophotometer using a 1 cm pathlength cuvette at room temperatu- re. LC-ESI mass spectra were recorded with a Bru- ker microTOF spectrometer. Matrix-assisted laser de- sorption/ionization time-of-light mass spectrometry (MALDI-TOF-MS) measurements were performed on a Bruker Daltonics micrOTOF. Positive ion and *Correspondence to: Vefa Ahsen, email: ahsen@gyte.edu.tr, fax: +90 262-305-31-01  SPP full member or  student member in good standing