Sulfuric Acid → 2-(4-Hydroxy-3-phenylbenzoyl)benzoic acid

HRID 1656555

反応式

HRID 1656555 の反応式
C1C=CC2[C:10]([C:18]3[CH:19]=[CH:20][C:21](O)=[CH:22][CH:23]=3)([C:11]3[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=3)[O:9]C(=O)C=2C=1.Cl.NO.[OH-].[K+].OS(O)(=O)=O.CC[O:37][C:38](C)=[O:39]>CCCCCC.O>[OH:17][C:14]1[CH:15]=[CH:16][C:11]([C:10]([C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][C:23]=2[C:38]([OH:37])=[O:39])=[O:9])=[CH:12][C:13]=1[C:11]1[CH:12]=[CH:13][CH:14]=[CH:15][CH:16]=1

参加物

8

反応物 5

HCID 1118Sulfuric AcidHCID 4764PhenolphthaleinHCID 8857Ethyl AcetateHCID 14797Potassium Hydroxide2 回HCID 443297Hydroxyamine hydrochloride2 回

生成物 1

HCID 1634472-(4-Hydroxy-3-phenylbenzoyl)benzoic acid収率 58.4%

試薬・触媒・溶媒 2

HCID 8058Hexane触媒HCID 962Water溶媒

反応条件

温度
100 °C

実験手順

In a 100 mL r.b. flask equiped with a short column there was added the disubstituted derivative of phenolphthalein (2a) (2.0 g, 0.00425 mol), hydroxylamine hydrochloride (0.34 g, 0.0049 mol), potassium hydroxide (1.428 g 0.0255 mol) and 50 mL of H2O, and the mixture was stirred at 100° C. in an oil bath. The blue reaction mixture became homogeneous when it reached boiling. Within half an hour the colour had changed to brown. Following the reaction by thin layer chromatography (TLC) (20% EtOAc in hexane+3 drops AcOH), a new product was observed, but not all the starting material reacted. After 4 hr. no change had been observed and another portion of hydroxylamine hydrochloride (1.15 eq.) and potassium hydroxide (6.0 eq.) was added. An hour later, tlc indicated that no starting material remained. The reaction mixture was cooled to room temperature and it was acidified dropwise with concentrated H2SO4. A yellow precipitate was obtained. The reaction was stirred at 100° C. over night to complete the hydrolysis. The reaction mixture turned brown. It was filtered, washed 3× with hot diluted H2SO4 and then with H2O. It was recrystallized 2× (EtOAc/charcoal) to give 0.8 g, (58.4% yield) of a white product; 3a: mp 273° C.; 1H NMR (200 MHz, DMSO-d6) d 10.63 (s, 1H, COOH), 7.96 (d, j=8.0 Hz, 1H, CH-6), 7.74-7.34 (m, 10H, ArH), 7.02 (d, j=8.0 Hz, 1H, CH-5'). MS (EI) m/e 318 (M+); Anal. Calcd for C20H14O4: C, 75.47; H, 4.40; Found: C, 75.46; H, 4.62. ##STR21##

後処理

  1. customflask equiped with a short column there
  2. customThe blue reaction mixture
  3. waitWithin half an hour the colour had changed
  4. customnot all the starting material reacted
  5. customAn hour
  6. temperatureThe reaction mixture was cooled to room temperature
  7. customA yellow precipitate was obtained
  8. stirringThe reaction was stirred at 100° C. over night
  9. customthe hydrolysis
  10. filtrationIt was filtered
  11. washwashed 3× with hot diluted H2SO4
  12. customIt was recrystallized 2× (EtOAc/charcoal)

出典と根拠

ORDレコード
ord-2c6a131026ae4f6c9f322b100323fa8b
出典データセット
uspto-grants-1993_10
特許番号
US05254663

関連ノート

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