Formaldehyde → (S,S)-2-[1-Methyl-4-(2-methyl-4H-3-thia-4,9-diazabenzo[f]azulen-10-yl)-piperazin-2-yl]-1-phenyl-ethanol

HRID 1350528노트

반응식

HRID 1350528 반응식
C=O.[CH3:3][C:4]1[S:13][C:12]2[NH:11][C:10]3[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=3[N:8]=[C:7]([N:18]3[CH2:23][CH2:22][NH:21][C@@H:20]([CH2:24][C@@H:25]([C:27]4[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=4)[OH:26])[CH2:19]3)[C:6]=2[CH:5]=1.[C:33](O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(Cl)Cl.C(=O)(O)[O-].[Na+]>[CH3:33][N:21]1[CH2:22][CH2:23][N:18]([C:7]2[C:6]3[CH:5]=[C:4]([CH3:3])[S:13][C:12]=3[NH:11][C:10]3[CH:14]=[CH:15][CH:16]=[CH:17][C:9]=3[N:8]=2)[CH2:19][C@@H:20]1[CH2:24][C@@H:25]([C:27]1[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=1)[OH:26]

참가 물질

6

반응물 3

HCID 712FormaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 135900337(S,S)-2-[4-(2-methyl-4H-3-thia-4,9-diaza-benzo[f]azulen-10-yl)-piperazin-2-yl)-1-phenyl-ethanol

생성물 1

HCID 136005585(S,S)-2-[1-Methyl-4-(2-methyl-4H-3-thia-4,9-diazabenzo[f]azulen-10-yl)-piperazin-2-yl]-1-phenyl-ethanol수율 42.6%

시약·촉매·용매 2

HCID 6344Dichloromethane용매HCID 516892Sodium Bicarbonate용매

실험 절차

Add formaldehyde (33 μL, 0.42 mmol, 37% in water) to a solution of (S,S)-2-[4-(2-methyl-4H-3-thia-4,9-diaza-benzo[f]azulen-10-yl)-piperazin-2-yl]-1-phenyl-ethanol (160 mg, 0.38 mmol) in methylene chloride (6 mL). Stir 15 min at ambient temperature. Add sodium triacetoxyborohydride (121 mg, 0.57 mmol) and stir 2 h at ambient temperature. Dilute with saturated sodium bicarbonate solution and extract with methylene chloride. Dry the extracts with sodium sulfate, filter and concentrate the filtrate. Purify by radial silica gel chromatography using a 2 mm plate and 2N ammonia in methanol-methylene chloride (1%–5%) as the eluent to give 70 mg (42%) of the title compound: mass spectrum (ion spray): m/z=433 (M+1), 431 (M−1). HR-MS calculated for C25H29N4OS: 433.2062. Found 433.2061. 1H NMR (DMSO-d6): δ 7.60 (s, 1H), 7.36–7.17 (m, 5H), 6.88–6.75 (m, 3H), 6.68 (br d, 1H), 6.35 (s, 1H), 5.34 (br d, 1H), 4.60–4.50 (m, 1H), 3.85 (br d, 1H), 3.70 (br d, 1H), 3.04–2.92 (m, 1H), 2.85–2.66 (m, 2H), 2.29 (s, 3H), 2.17 (s, 3H), 2.20–2.10 (m, 1H) 2.08–1.98 (m, 1H), 1.97–1.85 (m, 1H), 1.66–1.52 (m, 1H).

후처리

  1. extractionextract with methylene chloride
  2. dry with materialDry the extracts with sodium sulfate
  3. filtrationfilter
  4. concentrationconcentrate the filtrate
  5. customPurify by radial silica gel chromatography

출처 및 근거

ORD 기록
ord-fe41d7fa014b4aa0b3d92dbce2406f0a
출처 데이터셋
uspto-grants-2007_05
특허 번호
US07214673B2

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