p-Toluenesulfonic acid → 1-[2-(2,5-Diphenyl-pyrrol-1-ylimino)-1-methyl-propylideneamino]-2-naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester

HRID 411128Notes

Reaction equation

HRID 411128 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[C:9]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[N:8]([NH2:17])[C:7]=1[C:18]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[CH:21]=[CH:20][CH:19]=1)=[O:5])[CH3:2].[C:28]1([C:34]2[N:35]([N:45]=[C:46]([CH3:50])[C:47](=O)[CH3:48])[C:36]([C:39]3[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=3)=[CH:37][CH:38]=2)[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1.C1(C)C=CC(S(O)(=O)=O)=CC=1.S(NN)(C1C=CC(C)=CC=1)(=O)=O>C1(C)C=CC=CC=1.O>[CH2:1]([O:3][C:4]([C:6]1[CH:10]=[C:9]([C:11]2[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=2)[N:8]([N:17]=[C:47]([CH3:48])[C:46](=[N:45][N:35]2[C:34]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)=[CH:38][CH:37]=[C:36]2[C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[CH3:50])[C:7]=1[C:18]1[C:27]2[C:22](=[CH:23][CH:24]=[CH:25][CH:26]=2)[CH:21]=[CH:20][CH:19]=1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 6101p-Toluenesulfonic acid2×HCID 15303P-ToluenesulfonylhydrazideHCID 542720351-Amino-2-naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carboxylic acid ethyl esterHCID 571252783-(2,5-Diphenyl-pyrrol-1-ylimino)-butan-2-one

Product 1

HCID 723459061-[2-(2,5-Diphenyl-pyrrol-1-ylimino)-1-methyl-propylideneamino]-2-naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

A solution of 1-Amino-2-naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester (434 mg, 1.22 mmol) in toluene (7.2 mL) was treated with 3-(2,5-Diphenyl-pyrrol-1-ylimino)-butan-2-one (308 mg, 1.02 mmol) and p-toluene sulfonic acid (8 mg). A Dean Stark trap was attached, and the resulting solution heated to reflux under Ar with the azeotropic removal of water for 18 h, then another portion of p-toluene sulfonic acid (8 mg) was added and the azeotropic removal of water was continued for an additional 75 min. The solution was cooled to rt and concentrated in vacuo. The residue was dissolved in THF/Acetic acid (10/1) and treated with PS-TsNHNH2 resin (Argonaut Technologies, 1.039 g, 2.6 mmol). The suspension was stirred under Ar overnight, then filtered through a polyethylene frit, and concentrated in vacuo. The residue was purified by flash chromatography (SiO2, 50-100% CH2Cl2/heptane) to afford 1-[2-(2,5-Diphenyl-pyrrol-1-ylimino)-1-methyl-propylideneamino]-2-naphthalen-1-yl-5-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester a66 (240 mg, 37%): 11H NMR (DMSO, chemical shifts relative to TMS, 80° C.): 0.82 (t, 3H, J=7.3 Hz), 1.08 (s, 3H), 1.74 (s, 3H), 3.91 (q, 2H, J=6.9 Hz), 6.42 (s, 2H), 7.03 (s, 1H), 7.11 (d, 4H, J=7.18 (t, 4H, J=7.3 Hz), 7.22-7.25 (m, 2H), 7.32-7.37 (m, 5H), 7.39-7.41 (m, 2H), 7.44-7.47 (m, 2H), 7.53 (d, 1H, J=8.2 Hz), 7.93 (t, 2H, J=8.7 Hz).

Workup

  1. temperaturethe resulting solution heated
  2. customthe azeotropic removal of water
  3. concentrationconcentrated in vacuo
  4. dissolutionThe residue was dissolved in THF/Acetic acid (10/1)
  5. filtrationfiltered through a polyethylene frit
  6. concentrationconcentrated in vacuo
  7. customThe residue was purified by flash chromatography (SiO2, 50-100% CH2Cl2/heptane)

Sources & evidence

ORD record
ord-7d85c005e8f7466db386d4c6c1c8fb99
Source dataset
uspto-grants-2003_05
Patent number
US06559091B1

Reaction notes

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