Triethylamine → n-(2-Hydroxy-4-nitrophenyl)-n'-(3-methoxy-2-thienyl)urea

HRID 567972Notes

Reaction equation

HRID 567972 reaction equation
[CH3:1][O:2][C:3]1[CH:7]=[CH:6][S:5][C:4]=1C(O)=O.C([N:13]([CH2:16]C)CC)C.[NH2:18][C:19]1[CH:24]=[CH:23][C:22]([N+:25]([O-:27])=[O:26])=[CH:21][C:20]=1[OH:28].P(N=[N+]=[N-])(OC1C=CC=CC=1)(OC1C=CC=CC=1)=[O:30]>C1(C)C=CC=CC=1>[OH:28][C:20]1[CH:21]=[C:22]([N+:25]([O-:27])=[O:26])[CH:23]=[CH:24][C:19]=1[NH:18][C:16]([NH:13][C:4]1[S:5][CH:6]=[CH:7][C:3]=1[O:2][CH3:1])=[O:30]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 123414Diphenylphosphoryl azideHCID 14834753-Methoxythiophene-2-carboxylic acidHCID 49847212-Amino-5-Nitrophenol

Product 1

HCID 21184722n-(2-Hydroxy-4-nitrophenyl)-n'-(3-methoxy-2-thienyl)ureaYield 48%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
70 °C

Procedure

To a solution of 3-methoxy-2-thiophene carboxylic acid (example 11a, 200 mg, 1.27 mmol) in toluene, (PhO)2PON3 (0.33 mL) and triethylamine (1.1 equiv., 0.25 mL) were added. The reaction mixture was stirred at 70° C. for 2 hours and cooled down to room temperature then 2-amino-5-nitrophenol was added. The reaction mixture was stirred at 70° C. overnight. The reaction mixture was partitioned between 5% citric acid and ethyl acetate. The organic layer was separated and the aqueous layer was extracted three times with ethyl acetate. The organic extracts were combined, dried over MgSO4, filtered and concentrated under reduced pressure. Chromatography of the resulting solid on silica gel (hexane:ethyl acetate;1:1) gave the product (190 mg, 48%). 1H NMR (CD3OD/CDCl3): δ 8.38 (d, 1H, J=5.0 Hz), 7.85 (dd, 1H, J=5.0 Hz and J=1.25 Hz), 7.76 (d, 1H, J=2.5 Hz), 6.9 (s, 2H), 3.95 (s, 3H); EI-MS m/z 309 (M+H)+; Anal. (C12H11N3O5S) C, H, N.

Workup

  1. temperaturecooled down to room temperature
  2. stirringThe reaction mixture was stirred at 70° C. overnight
  3. customThe reaction mixture was partitioned between 5% citric acid and ethyl acetate
  4. customThe organic layer was separated
  5. extractionthe aqueous layer was extracted three times with ethyl acetate
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-3f4ff7a4b13841f9b9b4c0d151b53efc
Source dataset
uspto-grants-2001_01
Patent number
US06180675B2

Reaction notes

Loading…