4-Hydroxybenzoic Acid → 4-Hydroxy-N-(4-nitrophenyl)benzamide

HRID 6418

反応式

HRID 6418 の反応式
[OH:1][C:2]1[CH:10]=[CH:9][C:5]([C:6]([OH:8])=O)=[CH:4][CH:3]=1.[N+:11]([C:14]1[CH:19]=[CH:18][C:17]([N:20]=C=O)=[CH:16][CH:15]=1)([O-:13])=[O:12]>[O-]CC.[Na+].O>[OH:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]([NH:20][C:17]2[CH:18]=[CH:19][C:14]([N+:11]([O-:13])=[O:12])=[CH:15][CH:16]=2)=[O:8])=[CH:9][CH:10]=1

参加物

5

反応物 2

HCID 1354-Hydroxybenzoic Acid2 回HCID 66012Benzene, 1-isocyanato-4-nitro-2 回

生成物 1

HCID 193752734-Hydroxy-N-(4-nitrophenyl)benzamide

試薬・触媒・溶媒 2

HCID 2723922Sodium ethoxide触媒HCID 962Water溶媒

反応条件

温度
30 °C

実験手順

p-Hydroxybenzoic acid (59.05 grams, 0.4275 mole), sodium ethoxide catalyst (0.133 gram, 0.225% wt. of the p-hydroxybenzoic acid used) and N,N'-dimethylacetamide solvent (404 grams) are added to a reactor equipped with a reflux condenser and stirred under a nitrogen atmosphere at 80° C. p-Nitrophenylisocyanate (73.85 grams, 0.450 mole) is initially added in an aliquot of 25.00 grams, followed by 25.00 and 23-85 gram aliquots eleven then nine minutes later, respectively, and so as to maintain a 80° to 82° C. reaction temperature. After the last aliquot of p-nitrophenylisocyanate is added, heating of the reactor commenced and a 160° C. reaction temperature is achieved 24 minutes later. After three hours at the 160° C. reaction temperature, the reactor is cooled to 30° C. then the contents poured into one gallon of deionized water. A precipitated yellow powder is recovered via filtration of the aqueous slurry then dissolved into 1900 milliliters of boiling methanol and refluxed therein (65° C.). After cooling the methanol solution to 5° C. and maintaining therein for twelve hours, a first crop of pale yellow colored crystalline product is filtered off and dried at 110° C. under vacuum to a constant weight of 92.5 grams (79.6% isolated yield). No attempt was made to recover a second crop of crystalline product from the mother liquor. Fourier transform infrared spectrophotometric analysis of a nujol mull of a portion of the product on a sodium chloride plate revealed the presence of the expected secondary amide N--H stretching (solid state) at 3385 cm-1 (sharp), the secondary amide carbonyl stretching (solid state) at 1655 cm-1 (sharp), the hydroxyl group O--H stretching centered at 3232 cm-1 (broad) and the conjugated nitro group absorbances at 1537 and 1339 cm-1 (sharp). Proton magnetic resonance spectroscopy (250 MHz) further confirmed the product structure as -hydroxy-4'-nitrobenzanilide.

後処理

  1. additionare added to a reactor
  2. customequipped with a reflux condenser
  3. additionis initially added in an aliquot of 25.00 grams
  4. temperaturenine minutes later, respectively, and so as to maintain a 80° to 82° C.
  5. customreaction temperature
  6. temperatureheating of the reactor
  7. customcommenced and a 160° C.
  8. customreaction temperature
  9. customAfter three hours at the 160° C. reaction temperature
  10. filtrationA precipitated yellow powder is recovered via filtration of the aqueous slurry
  11. dissolutionthen dissolved into 1900 milliliters of boiling methanol
  12. temperaturerefluxed
  13. custom(65° C.)
  14. temperatureAfter cooling the methanol solution to 5° C.
  15. temperaturemaintaining
  16. waitfor twelve hours
  17. filtrationa first crop of pale yellow colored crystalline product is filtered off
  18. customdried at 110° C. under vacuum to a constant weight of 92.5 grams (79.6% isolated yield)
  19. customto recover a second crop of crystalline product from the mother liquor

出典と根拠

ORDレコード
ord-144d23a00694409eac516557c38a54b0
出典データセット
uspto-grants-1993_09
特許番号
US05248758

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