4-Hydroxybenzoic Acid → HCID 57136582, compound

HRID 1893117Notes

Reaction equation

HRID 1893117 reaction equation
[OH:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=O)=[CH:4][CH:3]=1.FC(F)(F)C(OC(=O)C(F)(F)F)=O.C(O)(=O)C1C=CC=CC=1.C1(C)C=CC(S([N:42]2[CH:46]=[CH:45][CH:44]=[CH:43]2)(=O)=O)=CC=1.N1C=CC=C1.OP(O)(O)=O>CC#N.C(Cl)Cl>[OH:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]([C:43]2[NH:42][CH:46]=[CH:45][CH:44]=2)=[O:8])=[CH:9][CH:10]=1

Participants

9

Reactant 6

HCID 1354-Hydroxybenzoic Acid2×HCID 243Benzoic AcidHCID 1004Phosphoric AcidHCID 8027PyrroleHCID 9845Trifluoroacetic anhydride3×HCID 6400871-Tosylpyrrole

Product 1

HCID 57136582HCID 57136582, compound

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To a stirred suspension of 4-hydroxybenzoic acid (5.50 g, 40.0 mmol) in CH3CN cooled to 0° C. was added trifluoroacetic anhydride (TFAA, 10 mL, 72.0 mmol). After 15 minutes the benzoic acid dissolved. To this cooled solution at 0° C. was added 1-(p-tolylsulfonyl)pyrrole (8.85 g, 40.0 mmol) followed by enough CH2Cl2 to dissolve the pyrrole at this temperature. An additional volume of trifluoroacetic anhydride (10 mL, 72.0 mmol) was added to the reaction mixture followed by H3PO4 (2 mL, 37.0 mmol) with rapid stirring. After the reaction mixture was stirred at room temperature for 12 hours, additional trifluoroacetic anhydride (6 mL, 43.2 mmol) and 4-hydroxybenzoic acid (4.00 g, 29.0 mmol) were added and stirring was continued for 12 hours. After this, the solvents were removed to dryness and the residue was suspended in 5% NaOH (250 mL) and stirred overnight. The suspension was removed by filtration and the filter cake was washed with 5% NaOH (250 mL). To the filtrate was added a saturated solution of NaHCO3 (200 mL) and the pH of the solution was rendered neutral by adding concentrated HCl. A pink microcrystalline material formed and was collected by filtration, washed with water and dried. Yield (2-(4-Hydroxybenzoyl)-pyrrole) 3.30 g, 44%. 1H NMR (500 MHz, CD2Cl2, 25° C.) δ 6.35 (m, 1H), 6.90 (m, 1H), 6.94 (d, 2H), 7.14 (m, 1H), 7.87 (d, 2H), 9.70 (bs, 1H).

Workup

  1. stirringstirring
  2. waitwas continued for 12 hours
  3. customAfter this, the solvents were removed to dryness
  4. stirringstirred overnight
  5. customThe suspension was removed by filtration
  6. washthe filter cake was washed with 5% NaOH (250 mL)
  7. additionTo the filtrate was added a saturated solution of NaHCO3 (200 mL)
  8. additionby adding concentrated HCl
  9. customA pink microcrystalline material formed
  10. filtrationwas collected by filtration
  11. washwashed with water
  12. customdried

Sources & evidence

ORD record
ord-e81acbc2d9404c50af8b17173bb559bc
Source dataset
uspto-grants-2013_08
Patent number
US08512879B2

Reaction notes

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