Hydrochloric Acid → 3-Methyl-5-phenyl-1,3-dihydro-benzo[e][1,4]diazepin-2-one

HRID 75252

反応式

HRID 75252 の反応式
C(OC(=O)[NH:7][CH:8]([C:10](=[O:26])[NH:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:18](=O)[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH3:9])(C)(C)C.Cl>C(Cl)(Cl)Cl>[CH3:9][CH:8]1[C:10](=[O:26])[NH:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=2[C:18]([C:19]2[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=2)=[N:7]1

参加物

4

反応物 2

HCID 313Hydrochloric AcidHCID 68524295[1-(2-Benzoyl-phenylcarbamoyl)-ethyl]-carbamic acid tert-butyl ester

生成物 1

HCID 110322973-Methyl-5-phenyl-1,3-dihydro-benzo[e][1,4]diazepin-2-one収率 83%

試薬・触媒・溶媒 1

HCID 6212Chloroform溶媒

実験手順

To a stirred solution of the benzophenone 109 (10.65 g 29.38 mmol) in CHCl3 (400 mL) at rt, hydrogen chloride gas was added in slowly. After 20 min, the addition was stopped and the solution was stirred overnight at rt. The reaction mixture was washed with a saturated solution of sodium bicarbonate (2×50 mL) and water (2×50 mL). The organic layer was concentrated under reduced pressure. The residual oil was dissolved in methanol-water (2:1, 500 mL) and the pH was adjusted to 8.5 by the addition of aqueous sodium hydroxide (1 N). The reaction mixture was stirred for 10 h at rt. The solution was concentrated under reduced pressure and water (100 mL) was added. The solution was extracted with CH2Cl2 (3×100 mL) and concentrated under reduced pressure. The crude solid 110 was purified by recrystallization from methanol/water to provide 110 (6.10 g, 83%). mp 160-162° C.; IR (KBr, cm−1) 3215, 3059, 2974, 2932, 1681, 1574, 1478, 1445, 1372, 1321, 1242, 1160, 1131; 1H NMR (CDCl3) δ 9.65 (s, 1 H), 7.54-7.13 (m, 9 H), 3.78 (q, J=6.5 Hz, 1 H), 1.78 (d, J=7.1 Hz 3H); MS (EI) m/e (relative intensity) 250 (M+, 40), 249 (83), 234 (15), 209 (75), 208 (76), 207 (100), 180 (17), 152 (19) 103 (23), 77 (40); [α]26D=290.2 (c 0.78, EtOAc).

後処理

  1. additionthe addition
  2. washThe reaction mixture was washed with a saturated solution of sodium bicarbonate (2×50 mL) and water (2×50 mL)
  3. concentrationThe organic layer was concentrated under reduced pressure
  4. dissolutionThe residual oil was dissolved in methanol-water (2:1, 500 mL)
  5. additionthe pH was adjusted to 8.5 by the addition of aqueous sodium hydroxide (1 N)
  6. stirringThe reaction mixture was stirred for 10 h at rt
  7. concentrationThe solution was concentrated under reduced pressure and water (100 mL)
  8. additionwas added
  9. extractionThe solution was extracted with CH2Cl2 (3×100 mL)
  10. concentrationconcentrated under reduced pressure
  11. customThe crude solid 110 was purified by recrystallization from methanol/water

出典と根拠

ORDレコード
ord-bef153c3f0f3485993b0433fb066682c
出典データセット
uspto-grants-2014_09
特許番号
US08835424B2

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