Water → HCID 69020975, compound

HRID 1865084Notes

Reaction equation

HRID 1865084 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[N:7]([CH3:20])[CH:8]=[C:9]([C:18]#[N:19])[C:10]=1[C:11]1[CH:16]=[CH:15][C:14]([OH:17])=[CH:13][CH:12]=1)=[O:5])[CH3:2].F[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=1[N+:28]([O-:30])=[O:29].C1OCCOCCOCCOCCOCCOC1.O>C(#N)C.C(Cl)Cl>[CH2:1]([O:3][C:4]([C:6]1[N:7]([CH3:20])[CH:8]=[C:9]([C:18]#[N:19])[C:10]=1[C:11]1[CH:16]=[CH:15][C:14]([O:17][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][C:23]=2[N+:28]([O-:30])=[O:29])=[CH:13][CH:12]=1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 962WaterHCID 2855718-Crown-6HCID 738951-Fluoro-2-nitrobenzeneHCID 69021586HCID 69021586, compound

Product 1

HCID 69020975HCID 69020975, compoundYield 69.3%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

Add together 4-cyano-3-(4-hydroxyphenyl)-1-methyl-1H-pyrrole-2-carboxylic acid ethyl ester (prepared in example E-11) (600 mg, 2.22 mmol), 1-fluoro-2-nitrobenzene (313 mg, 1.0 Eq.), potassium fluoride/alumina (322 mg, 2.5 Eq.), and 18-crown-6 (60 mg, 0.1 Eq.) in acetonitrile (25 mL) and stir at reflux for 18 hours under a nitrogen atmosphere. Cool mixture and add water and methylene chloride (50 mL each) and stir vigorously. Separate layers and wash the organic layer once with water, dry over potassium carbonate, filter, and concentrate under reduced vacuum to give 762 mg as a dark solid. Purify the material by silica gel chromatography (Chromatotron™) eluting with methylene chloride to provide 602 mg of the title compound as a yellow solid. Mass spectrum (m/e): 392.2 (M*+1): (Bruker 300) 1NMR δ (CDCl3) 7.93-8.00 (1H, d), 7.50-7.57 (1H, t), 7.35-7.40 (2H, d), 7.19-7.29 (2H, m), 7.03-7.13 (2H, m), 4.05-4.20 (2H, dd), 3.95-4.10 (3H, s), 1.00-1.10 (3H, t).

Workup

  1. temperatureat reflux for 18 hours under a nitrogen atmosphere
  2. temperatureCool mixture
  3. stirringstir vigorously
  4. washSeparate layers and wash the organic layer once with water
  5. dry with materialdry over potassium carbonate
  6. filtrationfilter
  7. concentrationconcentrate under reduced vacuum
  8. customto give 762 mg as a dark solid
  9. customPurify the material by silica gel chromatography (Chromatotron™)
  10. washeluting with methylene chloride

Sources & evidence

ORD record
ord-c9f9935040864abb89bdd2a2365808bc
Source dataset
uspto-grants-2009_12
Patent number
US07625932B2

Reaction notes

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