Trifluoroacetic acid → 21H,22H-Porphine

HRID 2111477Notes

Reaction equation

HRID 2111477 reaction equation
CC1C=C(C)C([CH:9]([C:15]2[NH:19][CH:18]=[CH:17][CH:16]=2)[C:10]2[NH:14][CH:13]=[CH:12][CH:11]=2)=C(C)C=1.C([NH:23]C(SC1C=CC(C=O)=CC=1)=O)C.C(O)(C(F)(F)F)=O.CC[N:44]([CH:48]([CH3:50])[CH3:49])[CH:45]([CH3:47])[CH3:46].[C:51]1(Cl)C(=O)[C:56](Cl)=[C:55](Cl)[C:53](=O)[C:52]=1Cl>C(Cl)Cl.C1COCC1.[C-]1(C2C=CC(C#CC3C=CC(C=O)=CC=3)=CC=2)C=CC=C1.[CH-]1C=CC=C1.[Fe+2]>[C:10]12[CH:9]=[C:15]3[N:19]=[C:18]([CH:17]=[CH:16]3)[CH:49]=[C:48]3[NH:44][C:45]([CH:46]=[CH:50]3)=[CH:47][C:56]3=[N:23][C:52]([CH:53]=[CH:55]3)=[CH:51][C:13]([NH:14]1)=[CH:12][CH:11]=2

Participants

9

Reactant 5

HCID 6422Trifluoroacetic acidHCID 8371ChloranilHCID 81531DiisopropylethylamineHCID 117803912,2'-(Mesitylmethylene)bis(1H-pyrrole)HCID 154789794-[s-(n-Ethylcarbamoyl)thio]-benzaldehyde

Product 1

HCID 13770524121H,22H-PorphineYield 36.1%

Reagents, catalysts & solvents 3

HCID 1317257561-(4-Ferrocenylphenyl)-2-(4-formylphenyl)acetyleneCatalystHCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

Samples of 5-mesityldipyrromethane (264 mg, 1.0 mmol), aldehyde 30 (195 mg, 0.50 mmol) and aldehyde 32 (105 mg, 0.50 mmol) were dissolved in CH2Cl2 (100 mL, undistilled) and then TFA (0.137 ml, 1.78 mmol) was added slowly over 30 s. The reaction mixture was stirred at rt for 30 min, and then DIEA (0.3 mL, 1.8 mmol) and a solution of p-chloranil (370 mg, 1.5 mmol) in THF (20 mL) was added and the mixture was stirred at rt for a further 6 h. Next the reaction mixture was evaporated to one-third of its initial volume and filtered through a silica pad (CH2Cl2/hexanes, 1:1). Fractions containing the second purple band were collected and chromatographed (silica, CH2Cl2/hexanes, 1:1; then CH2Cl2) to afford a slightly impure product. A second column (silica, CH2Cl2) was performed to obtain 56 mg of pure porphyrin (10.3%). 1H NMR δ −2.55 (s, 2H); 1.31 (t, J=7.2 Hz, 3H), 1.90 (s, 12H), 2.68 (s, 6H), 3.51 (m, 2H), 4.12 (5, H), 4.40 (s, 2H), 4.73 (s, 2H), 5.61 (brt, 1H), 7.34 (s, 6H), 7.56, 7.64 (AA′BB′, 4H), 7.9-8.4 (m, 8H), 8.7-9.0 (m, 8H); LD-MS obsd 1089.0, 1018.0 [M+ —CH3CH2NHCO]; FAB-MS obsd 1085.3766, calcd exact mass 1085.3790 (C71H59N5OSFe); λabs (CH2Cl2) 422, 516, 551, 590, 647 nm.

Workup

  1. stirringthe mixture was stirred at rt for a further 6 h
  2. customNext the reaction mixture was evaporated to one-third of its initial volume
  3. filtrationfiltered through a silica pad (CH2Cl2/hexanes, 1:1)
  4. additionFractions containing the second purple band
  5. customwere collected
  6. customchromatographed (silica, CH2Cl2/hexanes, 1:1
  7. customthen CH2Cl2) to afford a slightly impure product

Sources & evidence

ORD record
ord-d493528ab4634a49bdccd719ffc9acc2
Source dataset
uspto-grants-2009_04
Patent number
US07518905B2

Reaction notes

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