Benzaldehyde → HCID 135415342, compound

HRID 1955297Notes

Reaction equation

HRID 1955297 reaction equation
[CH:1](=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[F:9][C:10]1[C:14]([F:15])=[CH:13][NH:12][CH:11]=1.B(F)(F)F>C(Cl)Cl>[F:9][C:10]1[C:14]([F:15])=[C:13]2[C:1]([C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)=[C:13]3[N:12]=[C:11]([C:1]([C:2]4[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=4)=[C:13]4[NH:12][C:11](=[C:1]([C:2]5[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=5)[C:11]5[C:10]([F:9])=[C:14]([F:15])[C:13](=[C:1]([C:2]6[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=6)[C:11]=1[NH:12]2)[N:12]=5)[C:10]([F:9])=[C:14]4[F:15])[C:10]([F:9])=[C:14]3[F:15]

Participants

5

Reactant 3

HCID 240BenzaldehydeHCID 6356Boron trifluorideHCID 118046903,4-difluoro-1H-pyrrole

Product 1

HCID 135415342HCID 135415342, compoundYield 21%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Benzaldehyde (0.35 mL, 3.5 mmol), 3,4-difluoropyrrole (0.33 g, 3.2 mmol), and 250 mL of distilled CH2Cl2 were placed under N2 in a 500 mL round-bottom flask equipped with a magnetic stir bar. The reaction was stirred while BF3 etherate (0.5 mL, 3.9 mmol) was added via syringe. To monitor the reaction, aliquots were periodically removed from the reaction vessel, oxidized with DDQ, neutralized with pyridine, and chromatographed by silica gel TLC using CHCl3 as eluent. After 30 minutes, DDQ (1 g) and pyridine (5 mL) were added. The reaction was stirred for 12 hours, filtered through a short silica gel column using CH2Cl2 as eluent, and evaporated. The resulting solid was washed three times with 10 mL of pentane followed by three washes with 10 mL of ethanol. The product was recrystallized from toluene/hexane by layering to yield 127 mg of pure 2,3,7,8,12,13,17,18-octafluoro-5,10,15,20-tetraphenylporphyrin in 21% yield (first crop). A second crystallization using identical conditions yielded an additional 75 mg for a total isolated yield of 33%. The product is characterized by the following data: 1H NMR (360 MHz, CDCl3) δ 8.03 (d, 8H, J1 =6.7 Hz), 7.74 (m, 12H), -4.18 (s, 2H); 19F NMR (500 MHz, CDCl3, -50° C.) δ -141.1 (s, 4F), -146.4 (s, 4F); UV-vis (CH2Cl2) 402 (5.31), 499 (4.21), 532 (3.71), 581 (3.55), 637 (3.60); low resolution FAB MS 758 (calcd 758). Anal. Calcd for C44H22F8N4 : C, 69.66; H, 2.92; N, 7.38. Found: C, 69.43; H, 2.90; N, 6.95.

Workup

  1. customequipped with a magnetic stir bar
  2. additionwas added via syringe
  3. customthe reaction, aliquots
  4. customwere periodically removed from the reaction vessel
  5. customchromatographed by silica gel TLC
  6. additionDDQ (1 g) and pyridine (5 mL) were added
  7. filtrationfiltered through a short silica gel column
  8. customevaporated
  9. washThe resulting solid was washed three times with 10 mL of pentane
  10. customThe product was recrystallized from toluene/hexane

Sources & evidence

ORD record
ord-1410a60859884ce8b259dca83c34a46b
Source dataset
uspto-grants-2000_09
Patent number
US06124452

Reaction notes

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