CC BY ND NC 4.0 · SynOpen 2018; 02(02): 0133-0137
DOI: 10.1055/s-0036-1591998
paper
Copyright with the author

A Divergent Approach to β-Pyrazine-Fused meso-Tetraphenyl­diporphyrins

Raju Tiwari
,
Mahendra Nath*
R.T. is grateful to CSIR, New Delhi, India, for an SRF-NET Fellowship. Moreover, we gratefully acknowledge the award of a R&D grant from University of Delhi, Delhi, India.

Further Information

Publication History

Received: 14 March 2018

Accepted after revision: 05 April 2018

Publication Date:
09 May 2018 (online)

Abstract

We describe an alternative methodology for the synthesis of β-pyrazine-fused diporphyrins in high yields from 2-amino-5,10,15,20-tetraphenylporphyrin nickel(II) derivatives by using p-dodecylbenzenesulfonic acid as an efficient Brønsted acid catalyst in 1,4-dioxane at 90 °C. The structural characterization, material morphology and electronic properties of the products are reported.

Supporting Information

 
  • References

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  • 8 Synthesis of β-pyrazine-fused meso-tetraphenyldiporphyrin nickel(II) analogues 3 and 4To a solution of 2-amino-5,10,15,20-tetraphenylporphyrin nickel(II) (1; 68.5 mg, 0.1 mmol) or 2-amino-12,13-dibromo-5,10,15,20-tetraphenylporphyrin nickel(II) (2; 84.4 mg, 0.1 mmol) in 1,4-dioxane (10 mL), p-dodecylbenzenesulfonic acid (6.52 mg, 0.02 mmol) was added. The reaction mixture was stirred at 90 °C for one hour and the progress of reaction was monitored by TLC. After completion of the reaction, the mixture was diluted with ethyl acetate (40 mL) and washed with water (2 × 40 mL). The organic layer was collected and dried over anhydrous sodium sulfate. After filtration, the solvent was evaporated and the crude product was purified by silica gel column chromatography, eluting with 25% chloroform in hexane. The purified product was recrystallized from chloroform/methanol (1:1) solution.
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  • 10 Analytical data for β-pyrazine-fused 12,13,12′,13′-tetrabromo-5,10,15,20-tetraphenyldiporphyrin nickel(II) (4). Grey-green solid; yield: 68.7 mg (82%); IR (KBr): 2924, 1588, 1347, 1055, 1015, 791, 749, 697 cm–1; 1H NMR (400 MHz, CDCl3): δ = 8.59–8.26 (m, 8 H, β -pyrrolic H), 8.08–7.87 (m, 6 H, meso-phenyl H), 7.84–7.79 (m, 4 H, meso-phenyl H), 7.66–7.62 (m, 18 H, meso-phenyl H), 7.47–7.46 (m, 4 H, meso-phenyl H), 7.31–7.29 (m, 4 H, meso-phenyl H), 7.18–7.17 (m, 4 H, meso-phenyl H); UV/Vis (CH2Cl2): λ max (ε × 10–3) = 432 (366.8), 490 (433.7), 581 (91.5), 629 (96.1) nm; MALDI-TOF MS: m/z [M+] calcd for C88H48N10Ni2Br4: 1675.95; found: 1675.95.
  • 11 Crystallographic data for β-pyrazine-fused meso-tetraphenyldiporphyrin nickel(II) (3) have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication data CCDC-1043957
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