反応 #2161226

反応方程式

manganese chloride tetrahydrate

porphyrin

( 2 )

tetrakis(4-ethynylphenyl)porphyrin

→

manganese tetrakis(4-ethynylphenyl)porphyrin

収率 63.0%

溶媒

DMF

DMF

反応条件

後処理

1. 1
   その他as obtained in step 2) above and
2. 2
   温度The mixture was refluxed for 72 hours
3. 3
   その他After a return to ambient temperature, the solvent was evaporated off under reduced pressure
4. 4
   ろ過the manganese salts were eliminated by filtration over celite
5. 5
   その他The liquid filtrate was evaporated
6. 6
   workup.DISSOLUTIONthe residue was subsequently dissolved in 100 ml of ethanol
7. 7
   洗浄washed with 3×100 ml of water in order
8. 8
   その他After evaporation
9. 9
   workup.DISSOLUTIONthe residue was dissolved in chloroform
10. 10
    洗浄washed with a saturated aqueous solution of sodium chloride (3×100 ml) in order
11. 11
    洗浄finally washed with 2×100 ml of water in order
12. 12
    乾燥The organic phase was subsequently dried over sodium sulfate
13. 13
    その他the solvent was evaporated off
14. 14
    抽出During the first extraction with ethanol and water as solvents
15. 15
    その他a part of the porphyrin precipitated
16. 16
    ろ過This precipitate was filtered off
17. 17
    workup.DISSOLUTIONIt was subsequently redissolved in chloroform so that it
18. 18
    workup.ADDITIONcould be added to the organic phase during the washing with sodium chloride

実験手順

A solution of 5.5 g (27.8 mmol) of manganese chloride tetrahydrate (MnCl2.4H2O) in 160 ml of DMF was added portionwise to a solution of 1 g (1.4 mmol) of porphyrin TEPP (2) as obtained in step 2) above and dissolved in 200 ml of DMF. The mixture was refluxed for 72 hours. After a return to ambient temperature, the solvent was evaporated off under reduced pressure. The residue was taken up in 50 ml of chloroform and the manganese salts were eliminated by filtration over celite. The liquid filtrate was evaporated and the residue was subsequently dissolved in 100 ml of ethanol and washed with 3×100 ml of water in order to eliminate the TBAF. After evaporation, the residue was dissolved in chloroform and this organic phase was in turn washed with a saturated aqueous solution of sodium chloride (3×100 ml) in order to be sure that the axial ligand of the manganese is a chlorine, and finally washed with 2×100 ml of water in order to eliminate the traces of sodium chloride. The organic phase was subsequently dried over sodium sulfate and the solvent was evaporated off. During the first extraction with ethanol and water as solvents, a part of the porphyrin precipitated. This precipitate was filtered off and kept. It was subsequently redissolved in chloroform so that it could be added to the organic phase during the washing with sodium chloride. 700 mg (0.88 mmol; yield 63%) of manganese tetrakis(4-ethynylphenyl)porphyrin (MnCl-TEPP) (5) were obtained in the form of a purple/black-colored powder which is green in solution in chloroform.

出典