Phosphate → (S)-7,8-dihydro-2,9-dimethoxy-7-methyl-6-phenanthridinol trifluoromethanesulfonate

HRID 1457794ノート

反応式

HRID 1457794 の反応式
[F:1][C:2]([F:15])([F:14])[S:3]([O:6]S(C(F)(F)F)(=O)=O)(=[O:5])=[O:4].[CH3:16][O:17][C:18]1[CH:31]=[CH:30][C:29]2[NH:28][C:27](=O)[C:26]3[C@@H:25]([CH3:33])[CH2:24][C:23]([O:34][CH3:35])=[CH:22][C:21]=3[C:20]=2[CH:19]=1.C(C1C=CC=C(C(C)(C)C)N=1)(C)(C)C.P([O-])([O-])([O-])=O>ClCCl>[F:1][C:2]([F:15])([F:14])[S:3]([O:6][C:27]1[N:28]=[C:29]2[C:20](=[C:21]3[C:26]=1[C@@H:25]([CH3:33])[CH2:24][C:23]([O:34][CH3:35])=[CH:22]3)[CH:19]=[C:18]([O:17][CH3:16])[CH:31]=[CH:30]2)(=[O:5])=[O:4]

参加物

6

反応物 4

HCID 1061PhosphateHCID 67749Trifluoromethanesulfonic anhydrideHCID 685102,6-Di-tert-butylpyridineHCID 11043868(S)-7,8-dihydro-2,9-dimethoxy-7-methyl-6(5H)-phenanthridinone

生成物 1

HCID 18660709(S)-7,8-dihydro-2,9-dimethoxy-7-methyl-6-phenanthridinol trifluoromethanesulfonate収率 86.6%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
23 °C

実験手順

Trifluoromethanesulfonic anhydride (3.80 mL, 22.4 mmol, 1.10 equiv) was added via syringe to a suspension of (S)-7,8-dihydro-2,9-dimethoxy-7-methyl-6(5H)-phenanthridinone (10, 5.52 g, 20.3 mmol, 1 equiv) and 2,6-di-t-butylpyridine (6.10 mL, 27.1 mmol, 1.33 equiv) in dichloromethane (400 mL) at -78° C. The cold suspension was allowed to warm to 23° C. over 30 min and was stirred at that temperature for 15 min. Solids were observed to dissolve as the reaction proceeded. The reaction mixture was poured into aqueous phosphate buffer solution (pH 7, 0.05M in sodium hydrogen phosphate and 0.05M in potassium dihydrogen phosphate, 200 mL). The aqueous layer was separated and further extracted with two 200-mL portions of dichloromethane. The combined organic layers were dried over sodium sulfate and were concentrated in vacuo. The residue was purified by flash column chromatography (40% dichloromethane-hexanes) to provide (S)-7,8-dihydro-2,9-dimethoxy-7-methyl-6-phenanthridinol trifluoromethanesulfonate (ester) (12) as an off-white solid (mp 129.5°-130.5° C., 7.09 g, 86%).

後処理

  1. dissolutionto dissolve as the reaction
  2. customThe aqueous layer was separated
  3. extractionfurther extracted with two 200-mL portions of dichloromethane
  4. dry with materialThe combined organic layers were dried over sodium sulfate
  5. concentrationwere concentrated in vacuo
  6. customThe residue was purified by flash column chromatography (40% dichloromethane-hexanes)

出典と根拠

ORDレコード
ord-669febd64e70441eb5584bd179c39269
出典データセット
uspto-grants-1998_12
特許番号
US05849750

反応ノート

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