p-Toluenesulfonic acid → Dibenzyl 5,5'-[(3,4-diethyl-1H-pyrrole-2,5-diyl)bis(methylene)]bis[4-(3-methoxy-3-oxopropyl)-3-methyl-1H-pyrrole-2-carboxylate]

HRID 1755956Notes

Reaction equation

HRID 1755956 reaction equation
[CH2:1]([C:3]1[C:7]([CH2:8][CH3:9])=[CH:6][NH:5][CH:4]=1)[CH3:2].C(O[CH2:14][C:15]1[NH:16][C:17]([C:27]([O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)=[O:28])=[C:18]([CH3:26])[C:19]=1[CH2:20][CH2:21][C:22]([O:24][CH3:25])=[O:23])(=O)C.[C:37]1([CH3:47])[CH:42]=[CH:41][C:40](S(O)(=O)=O)=[CH:39][CH:38]=1>>[CH2:30]([O:29][C:27]([C:17]1[NH:16][C:15]([CH2:14][C:4]2[NH:5][C:6]([CH2:14][C:15]3[NH:16][C:17]([C:27]([O:29][CH2:47][C:37]4[CH:42]=[CH:41][CH:40]=[CH:39][CH:38]=4)=[O:28])=[C:18]([CH3:26])[C:19]=3[CH2:20][CH2:21][C:22]([O:24][CH3:25])=[O:23])=[C:7]([CH2:8][CH3:9])[C:3]=2[CH2:1][CH3:2])=[C:19]([CH2:20][CH2:21][C:22]([O:24][CH3:25])=[O:23])[C:18]=1[CH3:26])=[O:28])[C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=1

Participants

4

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 563951Benzyl 5-[(acetyloxy)methyl]-4-(3-methoxy-3-oxopropyl)-3-methyl-1H-pyrrole-2-carboxylateHCID 109095633,4-Diethylpyrrole

Product 1

HCID 10628875Dibenzyl 5,5'-[(3,4-diethyl-1H-pyrrole-2,5-diyl)bis(methylene)]bis[4-(3-methoxy-3-oxopropyl)-3-methyl-1H-pyrrole-2-carboxylate]Yield 61%

Conditions

Temperature
60 °C

Procedure

7C, FIG. 7A. In a 500 mL round bottom flask was placed 250 mL of ethanol from an unopened bottle and this was then purged with dry nitrogen for ten minutes. 3,4-Diethylpyrrole 7B (1.29 g, 0.01 mol) and 2-acetoxymethyl-5-benzyloxycarbonyl-4-methyl-3-methoxycarbonylethylpyrrole 7A (7.83 g, 0.02 mol) were added and the mixture heated until all of the pyrroles dissolved. p-Toluenesulfonic acid (65 mg) was added and the reaction temperature maintained at 60° C. The reaction slowly changed color from a clear yellow to a dark red with the product precipitating out of the solution as the reaction progressed. After ten hours the reaction was cooled to room temperature, the volume reduced to one half on a rotary evaporator, and then placed in the freezer for several hours. The product was collected by filtration, washed with a small amount of cold ethanol to afford 4.61 g of an off white fine powder (61%): 1H NMR (CDCl3, 250 MHz): δ1.14 (6H, t, CH2CH3), 2.23 (6H, s, pyrrole-CH3), 2.31 (4H, t, CH2CH2CO2CH3), 2.50 (4H, q, CH2CH3), 2.64 (4H, t, CH2CH2CO2CH3), 3.60 (1OH, br s, CH3CO2 -- and (pyrrole)2 -CH2), 4.44 (4H, br s, C6H5CH2), 6.99-7.02 (4H, m, aromatic), 7.22-7.26 (6H, m, aromatic), 8.72 (1H, s, NH), 10.88 (2H, br s, NH); 13C NMR (CDCl3, 250 MHz): δ10.97, 16.78, 17.71, 19.40, 22.07, 35.09, 51.46, 65.32, 117.37, 119.34, 122.14, 126.58, 126.79, 127.36, 128.19, 133.55, 136.62, 162.35, 173.49; CI MS (M+H)+ 750; HRMS 749.3676 (calc. for C44H51N3O8 : 749.3676).

Workup

  1. customIn a 500 mL round bottom flask was placed
  2. custom250 mL of ethanol from an unopened bottle and this was then purged with dry nitrogen for ten minutes
  3. dissolutiondissolved
  4. customThe reaction slowly changed color from a clear yellow to a dark red with the product
  5. customprecipitating out of the solution as the reaction
  6. temperatureAfter ten hours the reaction was cooled to room temperature
  7. customthe volume reduced to one half on a rotary evaporator
  8. waitplaced in the freezer for several hours
  9. filtrationThe product was collected by filtration
  10. washwashed with a small amount of cold ethanol

Sources & evidence

ORD record
ord-65d4afd942324607a8f0c47c2227e9e1
Source dataset
uspto-grants-1995_08
Patent number
US05439570

Reaction notes

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