to remove the solvent. After purification with column chromatography on silica gel using hexane-
toluene 3:2 as eluent, 600 mg of desired product were obtained. (yield 97%).
1H NMR (300 MHz, rt, CDCl3):δ= 7.97 (d, J = 8.7 Hz, 2H aromatic) 7.49 (d, J = 8.7 Hz, 2H aromatic),
3.91 (s, 3H, CH3), 0.26 (s, 9H, Si(CH3)3); IR (nujol, cm-1 2160 C≡C, 1732 C=O)
(c) 4-ethynylmethylbenzoate: 600 mg of 4-(trimethylsilyl)ethynylmethylbenzoate (2.58 mmol) were
dissolved in 12 ml of methanol and then 156 mg of anhydrous K2CO3 were added. The mixture was
stirred under argon atmosphere at room temperature for 3 hours and then diluted with
dichloromethane and washed 3 times with water. The aqueous phase was extracted with
dichloromethane and the organic phase dried over Na2SO4 and concentrated to afford 346 mg of
product, which was used without any purification, (yield 84%).1H NMR (300 MHz, rt, CDCl3): δ=
7.99 (d, J = 9.1 Hz, 2H aromatic) 7.54 (d, J = 9.1 Hz, 2H aromatic), 3.92 (s, 3H, CH3), 3.22 (s, 1H,
≡CH); IR (nujol cm-1, 2102 C≡C, 1700 C=O)
(d) 9(10),16(17),23(24)-Tri-tert-butyl-2-[ethynyl-(4-carboxymethyl)phenyl]phthalocyaninatozinc(II)
In argon atmosphere, 73 mg of a (0.084 mmol) were dissolved in 2 ml of Et3N and then 16 mg of c
(0.1 mmol), 1.2 mg of (PPh3)2PdCl2 (0.00168 mmol) and 0.16 mg of CuI (0.00084 mmol) were added.
The mixture was stirred for 5 hours in argon atmosphere and then it was concentrated to afford 137
mg of crude product. After purification with column chromatography using hexane-dioxane 9:1 and
1
4:1 as eluents, the desired product was obtained as a green solid. (75 mg, 99% yield). H NMR (300
MHz, rt, THF d8): δ= 9.42-8.86 (m, 8H, ring), 8.30-8.11 (m, 6H, phthalocyanine macrocycle and
benzoic ring), 7.93-7.87 (m, 2H, benzoic ring), 3.94 (s, 3H, CH3), 1.87 (s, 27H, C(CH3)3)
IR (KBr cm-1, 2206 C≡C,),UV-Vis (THF, nm): 671, 686; ISI/MS (m/z) [M+H+] 903.2-909.2 ;
elemental analysis: C54H46N8O2Zn·2C4H8O2(dioxane) (1060.39), calcd. C 70.16, H 6.08, N 10.56;
found C 70.20, H 6.15, N 10.01.
(I) 9(10),16(17),23(24)-Tri-tert-butyl-2-[ethynyl-(4-carboxy)phenyl]phthalocyaninatozinc(II)
20 mg of ester (0.022 mmol) were dissolved in 5 ml of a 1:1 THF-methanol solution and after the
addiction of 190 mg of NaOH dissolved in 5 ml of H2O the resultant mixture was refluxed under
stirring until the TLC showed the complete disappearance of the reagent. Then it was concentrated to
eliminate THF and methanol and the resulting aqueous phase was acidified to allow the precipitation
of the product which was collected by filtration and washed several times with water. The resulting 19
mg of crude were purified by column chromatography using silica gel as stationary phase and 4:1
hexane-dioxane and 1:1 chloroform-methanol as mobile phases and the blue-greenish solid obtained
1
was washed several times with water and methanol. (13 mg, yield 66.5%); H NMR (300 MHz, rt,
THF d8): δ= 9.86-7.67 (m, 16H, aromatics), 1.67 (s, 27H, C(CH3)3)
IR (nujol cm-1, 2203 C≡C)
UV-Vis (THF, nm): 671, 685