Artur Vashurin, Vladimir Maizlish, Ilya Kuzmin, Oleg Petrov, Mikhail Razumov, Svetlana

Aza-substitution, benzo-annulation effects and catalytic activity of β-octaphenyl-substituted tetrapyrrolic macroheterocyclic cobalt complexes. I. Heterogeneous catalysis

Artur Vashurin, Vladimir Maizlish, Ilya Kuzmin, Oleg Petrov, Mikhail Razumov, Svetlana Pukhovskaya, Oleg Golubchikov and Oscar Koifman

Cobalt(II) complex of 2,3,7,8,12,13,17,18-octaphenylporphyrine (Co(II)P) was synthesized according to the method recommended in [1]. To a stirred mixture of LiAlH4 (5 mmol) in THF (30 ml) was added Ethyl 3,4-diphenylpyrrole-2-carboxylate (3 mmol) in THF (5 ml) at 7 °C. The reaction mixture was stirred for 1 h at this temperature then poured into saturated aqueous NH4Cl, and extracted with CH2Cl2 (100 ml × 3). To the combined extracts was added toluene-p-sulfonic acid (0.02 g), and the resulting solution was stirred for 12 h at room temperature and then chroranil (0.4 g) was added. The mixture was stirred for 8 h, and washed with 5% aqueous sodium hydrogen carbonate, and the organic layer was dried with anhydrous sodium carbonate. After evaporation, column chromatography of the residue (silica gel, CH2Cl2) gave H2P. Yield 0.17 g (24 %); M/z 917.4 [M+]. The cobalt complex of H2P was prepared on treatment with a saturated solution of Co(OAc)2 in acetic acid. Elemental analysis for C68H44СoN4,%: С 83.68; H 4.54; N 5.74. Found С 83.46; H 4.57; N 5.82.

Cobalt(II) complex of 2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetraazaporphyrine(Co(II)Pz) was synthesized according to the method recommended in [2-4]. Mixture of diphenylmaleinitrile 2.3 g (0.01 mol), 0.25 g (4.6 mmol) of cobalt acetate, 10 mg of iodine and 10 mg of ammonium molibdate was heated to 302 °C under nitrogen. When the diphenylmaleinitrile began subliming up the walls of the tube, 0.25 mL of toluene was added. The refluxing of the toluene recycled the diphenylmaleinitrile into the reaction mixture. The reaction mixture formed a solid green mass after 1 h and was heated an additional 24 h. The product was then heated to 420 °C in vacuum to remove the unreacted dinitrile. Yield 130 mg (6%). M/z 975.9 [M+]. Elemental analysis for C64H40СoN8, %: С 78.44; H 4.11; N 11.43. Found С 78.23; H 4.16; N 11.45.

Cobalt(II) complex of 2,3,910,16,17,23,24-octaphenyltetrabenzoporphyrine (Co(II)BP) was synthesized according to the method recommended in [5]. The mixture of 0.3 g (0.025 mmol) of 4,5-diphenyl phthalic acid imide, 0.22 g (1.01 mmol) of cobalt acetate and 0.4 g (4.88 mmol) of sodium acetate was heated for 3 hours under 302 °C and blowing with nitrogen. Further the mixture was cooled to 25 °C and washed with water-ethanol solution (1:1). The dried solid was dissolved in chloroform and chromatographed. The yield is 0.02 g (8%). M/z 1117.4 [M++Н]. Elemental analysis for C84H52СoN4, %: С 85.77; H 4.46; N 4.76. Found С 85.64 ; H 4.53 ; N 4.81.

Cobalt(II) complex of 2,9,16,23-tetraphenylphthalocyanine (Co(II)Pc) was synthesized according to the method recommended in [6]. The pounded mixture of 0.223 g (1 mmol) of 4-phenylphthalimide, 0.024 g (0.45 mmol) ammonia chloride, 0.29 g (4.83 mmol) of urea, 0.07 g (0.28 mmol) of tetrahydrous cobalt acetate was maintained for 3 hours under the temperature of 181-185 °C in presence of ammonia molybdate as catalyst. Then the reaction mixture was triturated again and washed with 5% solution of hydrochloric acid to no solids in the filtrate. Further there were washing with water to neutral medium. The precipitate was dried under the vacuum and 97°C. The yield is 0.1 g (45.7 %). Elemental analysis for C56H32Сo N8, %: С 76.8; H 3.68; N 12.79. Found С 76.15; H 3.73; N 12.85.

Cobalt(II) complex of 2,3,910,16,17,23,24-octaphenyltetrapyrazinoporphyrazine(Co(II)PPz) was synthesized according to the [7-8]. Free ligand was dissolved in dimethylsulfoxide and hundredfold excess of cobalt acetate was added. Reaction mixture was heated up to 40 °C and maintained for 60 minutes. Next, the solution was evaporated. Dry solid was washed with distilled water to remove unreacted salt. There was hypsochromic shift of absorption band in visible range of spectrum for 30 nm (λ 635 nm) while the CoPPz is formed. This indicates the formation of metal complex. Elemental analysis for C72H40Сo N16, %: С 72.78; H 3.39; N 18.86;. Found С 72.15; H 3.63; N 18.97.

Reaction ofoxidation of DTC.

Disulfide formation was monitored with FT-IR spectra, and 1H NMR, and 13C NMR. 1H NMR of DTC to oxidation (500 MHz, D2O), (δ:ppm): 4.34 (m, J = 15 Hz, 4H, CH2); 1.39 (t, J = 5 Hz, 6H, CH3).13C NMR of DTC to oxidation (100 MHz): δ 11.65, 27.50, 49.08, 205.02. IR of DTC to oxidation IR (KBr): υ/cm-1 2979 (-CH3 υas), 2847 (-CH2- υas), 1476 (-CH2- δ), 1378 (-C-N st), 1269 (-C =S st), 1075, (d, -C-S).

During oxidation of DTC the formation of diethylcarbamothioylsulfanyl-N,N-diethylcarbamodithioate (Thiuram E) is observed. 1H NMR of Thiuram E obtained by DTC oxidation (500 MHz, CDCl3), (δ:ppm): 3.71-3.77 (m, 8H, CH2); 1.29-1.23 (m, 12H, CH3). 13C NMR of Thiuram E obtained by DTC oxidation (100 MHz): δ 10.49, 25.72, 52.04, 51.26, 190.05. IR of Thiuram E obtained by DTC oxidation IR (KBr): υ/cm-1 2974 (-CH3 υas), 2861 (-CH2- υas), 1505 (-CH2- δ), 1380 (-C-N st), 1273 (-C=S st), 1143, 995 (-S-S-).

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