Methanol → HCID 136396477, compound

HRID 1064221Notes

Reaction equation

HRID 1064221 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=1[C:7]1[C:26]2[NH:27][C:23](=[CH:24][CH:25]=2)[C:22]([C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][N:29]=2)=[C:21]2[N:34]=[C:18]([CH:19]=[CH:20]2)[C:17]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][N:36]=2)=[C:16]2[NH:41][C:13]([CH:14]=[CH:15]2)=[C:12]([C:42]2[CH:47]=[CH:46][CH:45]=[CH:44][N:43]=2)[C:11]2=[N:48][C:8]=1[CH:9]=[CH:10]2.[C:49]12[CH:72]=C3N=C(C=C3)C=C3NC(C=C3)=CC3=NC(C=C3)=CC(N1)=C[CH:50]=2.CO.C(Cl)(Cl)Cl>C(Br)C=C>[CH2:7]([C:33]1[C:28]([C:22]2[C:23]3[NH:27][C:26](=[CH:25][CH:24]=3)[C:7]([C:2]3[C:3]([CH2:6][CH:5]=[CH2:4])=[CH:4][CH:5]=[CH:6][N:1]=3)=[C:8]3[N:48]=[C:11]([CH:10]=[CH:9]3)[C:12]([C:42]3[C:47]([CH2:72][CH:49]=[CH2:50])=[CH:46][CH:45]=[CH:44][N:43]=3)=[C:13]3[NH:41][C:16]([CH:15]=[CH:14]3)=[C:17]([C:35]3[C:40]([CH2:10][CH:9]=[CH2:8])=[CH:39][CH:38]=[CH:37][N:36]=3)[C:18]3=[N:34][C:21]=2[CH:20]=[CH:19]3)=[N:29][CH:30]=[CH:31][CH:32]=1)[CH:2]=[CH2:3]

Participants

6

Reactant 4

HCID 887Methanol2×HCID 6212ChloroformHCID 135458625HCID 135458625, compoundHCID 13770524121H,22H-Porphine

Product 1

HCID 136396477HCID 136396477, compoundYield 78%

Reagents, catalysts & solvents 1

HCID 7841Allyl bromideSolvent

Conditions

Temperature
100 °C

Procedure

In an oven-dried flask under argon, 100 mg tetrakis(2-pyridyl)porphyrin (2-PyP) was dissolved in 5 mL allyl bromide, and reaction was heated at 100° C. for 16 hours. The reaction mixture was heated at 100° C. for 8 hours. Two methods were used to monitor the completion of the reaction. First, the shift of the porphyrin Soret band from λmax=412 nm (methanol) to λmax=418 nm (methanol) was monitored. A second method involved partition of an aliquot of the reaction mixture between H2O and CHCl3 whereby a complete reaction showed no color in the CHCl3 layer. Upon completion of the reaction, the allyl bromide was distilled off under high vacuum, and the residue was triturated with ethyl ether (Et2O). Chromatography was performed on Sephadex LH-20 (column dimensions were 2×20 cm) using methanol as the eluent and fractions that showed porphyrin with λmax=418 nm were retained. Compound VIII was produced as a shiny purple solid, in 78% yield. Absorbance data included the following: UV-vis: λmax (nm) (log10εo) 418(5.29) 512 (4.50) 587(4.32). Electrospray mass spectrometry (ES-MS) showed a molecular ion at 782 (M-4 Br).

Workup

  1. customreaction
  2. temperatureThe reaction mixture was heated at 100° C. for 8 hours
  3. customthe completion of the reaction
  4. customA second method involved partition of an aliquot of the reaction mixture between H2O and CHCl3 whereby
  5. customa complete reaction
  6. customUpon completion of the reaction
  7. distillationthe allyl bromide was distilled off under high vacuum
  8. customthe residue was triturated with ethyl ether (Et2O)

Sources & evidence

ORD record
ord-5c8624785a5e40a88e4577e25885b79d
Source dataset
uspto-grants-2005_11
Patent number
US06969707B2

Reaction notes

Loading…