Potassium Phosphate, Tribasic → HCID 135964263, compound

HRID 1184934Notes

Reaction equation

HRID 1184934 reaction equation
Br[C:2]1[C:3]2[CH:4]=[CH:5][C:6]([N:43]=2)=[C:7]([C:34]2[C:39]([CH3:40])=[CH:38][C:37]([CH3:41])=[CH:36][C:35]=2[CH3:42])[C:8]2[NH:12][C:11]([CH:13]=[C:14]3[N:33]=[C:17]([C:18]([C:24]4[C:29]([CH3:30])=[CH:28][C:27]([CH3:31])=[CH:26][C:25]=4[CH3:32])=[C:19]4[NH:23][C:22]=1[CH:21]=[CH:20]4)[CH:16]=[CH:15]3)=[CH:10][CH:9]=2.[O-]P([O-])([O-])=O.[K+].[K+].[K+].[C:52]([NH:55][C:56]1[CH:61]=[CH:60][C:59](B(O)O)=[CH:58][CH:57]=1)(=[O:54])[CH3:53]>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1COCC1>[C:52]([NH:55][C:56]1[CH:61]=[CH:60][C:59]([C:2]2[C:3]3[CH:4]=[CH:5][C:6]([N:43]=3)=[C:7]([C:34]3[C:35]([CH3:42])=[CH:36][C:37]([CH3:41])=[CH:38][C:39]=3[CH3:40])[C:8]3[NH:12][C:11]([CH:13]=[C:14]4[N:33]=[C:17]([C:18]([C:24]5[C:25]([CH3:32])=[CH:26][C:27]([CH3:31])=[CH:28][C:29]=5[CH3:30])=[C:19]5[NH:23][C:22]=2[CH:21]=[CH:20]5)[CH:16]=[CH:15]4)=[CH:10][CH:9]=3)=[CH:58][CH:57]=1)(=[O:54])[CH3:53]

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 27346574-Acetamidophenylboronic acidHCID 178424431HCID 178424431, compound

Product 1

HCID 135964263HCID 135964263, compoundYield 73%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolvent

Procedure

To a flask was added 157 mg (0.250 mmol) of 10-bromo-5,15-bis(2,4,6-trimethylphenyl)porphyrin, (6), 1.06 g (5.00 mmol) of potassium phosphate tribasic, 314 mg (1.76 mmol) of 4-acetamidophenylboronic acid (supplied by Acros), and 70 mL of THF. The suspension was flushed with argon for 10 min, and then 39 mg (0.025 mmol) of tetrakis(triphenylphosphine)palladium(0) was added and the argon flushing procedure continued for an additional 10 min. The reaction mixture was then warmed to reflux under an argon atmosphere for 48 h. The solvent was evaporated at reduced pressure, the residue was redissolved in dichloromethane and washed with water, the organic phase was dried over sodium sulfate, and the solvent was once again evaporated at reduced pressure. The crude product was chromatographed on silica gel (dichloromethane/1% acetone) to give 124 mg (73% yield) of the desired porphyrin. 1H NMR (300 MHz) δ−2.89 (2H, s, N—H), 1.84 (12H, s, Ar—CH3), 2.33 (3H, s, acetyl-CH3), 2.67 (6H, s, Ar—CH3), 7.29 (4H, s, Ar—H), 7.47 (1H, s, N—H), 7.85 (2H, d, J=8 Hz, Ar—H), 8.15 (2H, d, J=8 Hz, Ar—H), 8.72 (2H, d, J=5 Hz, β-H), 8.82 (4H, d, J=5 Hz, β-H), 9.26 (2H, d, J=5 Hz, β-H), 10.11 (1H, s, meso-H); MALDI-TOF-MS m/z calcd for C46H41N5O1 679.33, obsd 679.33.

Workup

  1. customThe suspension was flushed with argon for 10 min
  2. temperatureThe reaction mixture was then warmed
  3. temperatureto reflux under an argon atmosphere for 48 h
  4. customThe solvent was evaporated at reduced pressure
  5. dissolutionthe residue was redissolved in dichloromethane
  6. washwashed with water
  7. dry with materialthe organic phase was dried over sodium sulfate
  8. customthe solvent was once again evaporated at reduced pressure
  9. customThe crude product was chromatographed on silica gel (dichloromethane/1% acetone)

Sources & evidence

ORD record
ord-1a8bcda5379d4d04a4ad7278864792d4
Source dataset
uspto-grants-2014_03
Patent number
US08669359B2

Reaction notes

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