Pyridine → HCID 67763221, compound

HRID 1077995Notes

Reaction equation

HRID 1077995 reaction equation
[CH2:1]([O:4][C:5](=[O:31])[CH2:6][O:7][C:8]1[CH:13]=[CH:12][C:11]([CH2:14][O:15][C:16]2[CH:21]=[CH:20][C:19]([C:22](=[O:29])[C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[C:18]([NH2:30])[CH:17]=2)=[CH:10][CH:9]=1)[CH:2]=[CH2:3].N1C=CC=CC=1.[C:38]1([CH2:51][O:52][C:53](Cl)=[O:54])[C:50]2[CH2:49][C:48]3[C:43](=[CH:44][CH:45]=[CH:46][CH:47]=3)[C:42]=2[CH:41]=[CH:40][CH:39]=1>C(Cl)Cl>[CH2:1]([O:4][C:5](=[O:31])[CH2:6][O:7][C:8]1[CH:9]=[CH:10][C:11]([CH2:14][O:15][C:16]2[CH:21]=[CH:20][C:19]([C:22](=[O:29])[C:23]3[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=3)=[C:18]([NH:30][C:53]([O:52][CH2:51][C:38]3[C:50]4[CH2:49][C:48]5[C:43](=[CH:44][CH:45]=[CH:46][CH:47]=5)[C:42]=4[CH:41]=[CH:40][CH:39]=3)=[O:54])[CH:17]=2)=[CH:12][CH:13]=1)[CH:2]=[CH2:3]

Participants

5

Reactant 3

HCID 1049PyridineHCID 14261773Fluorenylmethyl chloroformateHCID 53904800HCID 53904800, compound

Product 1

HCID 67763221HCID 67763221, compoundYield 79%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

4-(3-Amino-4-benzoylphenoxymethyl)phenoxyacetic acid allyl ester (4.74 g, 11.4 mmol) and pyridine (1.09 g, 13.7 mmol, 1.2 equiv) were dissolved in 60 mL of CH2Cl2. The resulting yellow solution was cooled to 0° C., and fluorenylmethoxycarbonyl chloride (2.65 g, 1.14 mmol, 1.05 equiv) was added. The resulting solution was stirred at 0° C. for 15 min and then at ambient temperature for 1 h. The solution was diluted with CH2Cl2 (150 mL), extracted twice with 1N aqueous sodium bisulfate (100 mL), once with dilute aqueous sodium chloride (100 mL), and then concentrated to give a yellow foam. The unpurified product was crystallized from CH2Cl2 and hexanes to give 4.87 g (79% yield) purified material as a white solid: mp 96.5°-97.5° C. Rf 0.45 (CH2Cl2); IR (film from CH2Cl2, partial) 3230(b), 1740, 1610, 1575 cm-1 ; 1H NMR (300 MHz, CDCl3) δ 4.32 (t, 1, J=7.4), 4.44 (s, 1, J=0.5), 4.71 (dd, 2, J=1.2, 5.9), 5.11 (s, 2), 5.26 (dd, 1, J=1.2, 10.4), 5.30 (dd, 1, J=1.4, 17.2), 5.85-598 (m, 2), 6.58 (dd, 2, J=2,5m 8.9) 6.92 (d, 2, J=8.8, 6.92 (q, 2, J=4.8, 9.6), 7.30-7.59 (m, 8), 7.63-7.70 (m,5), 7.76 (d, 2, J=8.9), 7.77 (d, 2, J=7.5), 8.29 (d, 1, J=2.3). 13C NMR (75.5 MHz, CDCl3) δ 47.3, 65.6, 66.2, 67.9, 70.0, 104.4, 109.6, 115.2, 115.8, 119.5, 120.4, 125.6, 127.5, 128.1, 128.8, 129.6, 129.8, 131.7, 131.9, 137.6, 140.0, 141.6, 144.1, 144.6, 154.1, 158.5, 164.1, 167.8, 199.1. Anal. Calcd for C40H33NO7 : C, 75.10; H, 5.20; N, 2.19. Found: C, 75.21; H, 5.33; N, 2.28.

Workup

  1. waitat ambient temperature for 1 h
  2. extractionextracted twice with 1N aqueous sodium bisulfate (100 mL), once with dilute aqueous sodium chloride (100 mL)
  3. concentrationconcentrated
  4. customto give a yellow foam
  5. customThe unpurified product was crystallized from CH2Cl2 and hexanes
  6. customto give 4.87 g (79% yield)
  7. custompurified material as a white solid

Sources & evidence

ORD record
ord-6daec5809fac4d91a6a6945f2903294e
Source dataset
uspto-grants-1996_08
Patent number
US05545568

Reaction notes

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