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 1604725ノート

反応式

HRID 1604725 の反応式
[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

参加物

4

反応物 3

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

生成物 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]収率 61%

反応条件

温度
60 °C

実験手順

7C, FIG. 7. 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, a, pyrrole-CH3), 2.31 (4H, t, CH2CH2CO2CH3), 2.50 (4H, q, CH2CH3), 2.64 (4H, t, CH2CH2CO2CH3), 3.60 (10H, 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).

後処理

  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

出典と根拠

ORDレコード
ord-06e3a350537a4e558b110881611b97a0
出典データセット
uspto-grants-1999_11
特許番号
US05994535

反応ノート

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