Water → Zinc(II) 5,10,15,20-Tetrakis[m-(S-acetylthiomethyl)phenyl]porphyrin

HRID 431401Notes

Reaction equation

HRID 431401 reaction equation
[C:1]([S:4][CH2:5][C:6]1[CH:7]=[C:8]([C:12]2[C:13]3[NH:17][C:16]([C:18]([C:58]4[CH:63]=[CH:62][CH:61]=[C:60]([CH2:64][S:65][C:66](=[O:68])[CH3:67])[CH:59]=4)=[C:19]4[N:57]=[C:22]([C:23]([C:46]5[CH:51]=[CH:50][CH:49]=[C:48]([CH2:52][S:53][C:54](=[O:56])[CH3:55])[CH:47]=5)=[C:24]5[NH:45][C:27](=[C:28]([C:34]6[CH:39]=[CH:38][CH:37]=[C:36]([CH2:40][S:41][C:42](=[O:44])[CH3:43])[CH:35]=6)[C:29]6[CH:30]=[CH:31][C:32]=2[N:33]=6)[CH:26]=[CH:25]5)[CH:21]=[CH:20]4)=[CH:15][CH:14]=3)[CH:9]=[CH:10][CH:11]=1)(=[O:3])[CH3:2].[Zn:69](OC(C)=O)OC(C)=O.O.O.O>C(Cl)(Cl)Cl.CO>[Zn+2:69].[C:66]([S:65][CH2:64][C:60]1[CH:59]=[C:58]([C:18]2[C:16]3[NH:17][C:13]([C:12]([C:8]4[CH:9]=[CH:10][CH:11]=[C:6]([CH2:5][S:4][C:1](=[O:3])[CH3:2])[CH:7]=4)=[C:32]4[N:33]=[C:29]([C:28]([C:34]5[CH:39]=[CH:38][CH:37]=[C:36]([CH2:40][S:41][C:42](=[O:44])[CH3:43])[CH:35]=5)=[C:27]5[NH:45][C:24](=[C:23]([C:46]6[CH:51]=[CH:50][CH:49]=[C:48]([CH2:52][S:53][C:54](=[O:56])[CH3:55])[CH:47]=6)[C:22]6[CH:21]=[CH:20][C:19]=2[N:57]=6)[CH:25]=[CH:26]5)[CH:30]=[CH:31]4)=[CH:14][CH:15]=3)[CH:63]=[CH:62][CH:61]=1)(=[O:68])[CH3:67]

Participants

6

Reactant 3

HCID 962WaterHCID 1354519285,10,15,20-Tetrakis[m-(s-acetylthiomethyl)phenyl]porphyrinHCID 178476752HCID 178476752, compound

Product 1

HCID 137182967Zinc(II) 5,10,15,20-Tetrakis[m-(S-acetylthiomethyl)phenyl]porphyrin

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6212ChloroformSolvent

Procedure

A mixture of 16.2 mg of 29 (16.7 mol) in 20 mL of CHCl3 and a solution of 80.0 mg of Zn(OAc)2.2H2O (365 μmol) in 5 mL of methanol were combined and stirred at ambient temperature. After 2 h the metalation was completed (checked by fluorescence excitation spectroscopy) and 40 mL of H2O was added. The phases were separated and the organic layer was washed three times with 5% NaHCO3 and dried (Na2SO4). The solvents were removed under reduced pressure. Column chromatography over flash silica gel with CH2Cl2/hexanes (4:1) gave the title compound as a purple solid in quantitative yield. IR (neat): {tilde over (v)}=2922 (w, CH), 2849 (w, CH), 1690 (s, CO), 1655 (m, arom. C═C), 1600 (w, arom. C═C), 1478 (w), 1420 (w), 1338 (w), 1208 (m), 1131 (m), 1067 (w), 1002 (m), 955 (w), 932 (w), 794 (m), 717 (m); 1H NMR (300.5 MHz, CDCl3): δ=2.30 (s, 12H, CH3), 4.31 (s, 8H, CH2), 7.62-7.69 (m, 8H, ArH), 8.05-8.13 (m, 8H, ArH), 8.92 (s, 8H, β-pyrrole); LD-MS calcd av mass 1028.15 (C56H44N4l O4S4Zn), obsd 1028.8, 986.6 [M+—COCH3], 954.7 [M+—SCOCH3], 911.13 [M+—SCOCH3—COCH3], 880.4 [M+−2 SCOCH3], 838.8 [M+−2 SCOCH3—COCH3], 805.3 [M+−3 SCOCH3]; λabs (toluene) 424, 550, 589 nm; λem (toluene) 597, 647 nm.

Workup

  1. customThe phases were separated
  2. washthe organic layer was washed three times with 5% NaHCO3
  3. dry with materialdried (Na2SO4)
  4. customThe solvents were removed under reduced pressure

Sources & evidence

ORD record
ord-819447d50ac64f149b7d00aefd87fa13
Source dataset
uspto-grants-2003_12
Patent number
US06657884B2

Reaction notes

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