Hydrogen Peroxide → (+/-)-5-[({1-[3-(1-Methylethyl)-1,2,4-oxadiazol-5-yl]-4-piperidinyl}methyl)oxy]-2-[4-(methylsulfinyl)phenyl]pyridine

HRID 423669ノート

反応式

HRID 423669 の反応式
[CH3:1][CH:2]([C:4]1[N:8]=[C:7]([N:9]2[CH2:14][CH2:13][CH:12]([CH2:15][O:16][C:17]3[CH:18]=[CH:19][C:20]([C:23]4[CH:28]=[CH:27][C:26]([S:29][CH3:30])=[CH:25][CH:24]=4)=[N:21][CH:22]=3)[CH2:11][CH2:10]2)[O:6][N:5]=1)[CH3:3].[OH:31]O>FC(F)(F)C(O)C(F)(F)F.C(Cl)Cl>[CH3:3][CH:2]([C:4]1[N:8]=[C:7]([N:9]2[CH2:10][CH2:11][CH:12]([CH2:15][O:16][C:17]3[CH:18]=[CH:19][C:20]([C:23]4[CH:24]=[CH:25][C:26]([S:29]([CH3:30])=[O:31])=[CH:27][CH:28]=4)=[N:21][CH:22]=3)[CH2:13][CH2:14]2)[O:6][N:5]=1)[CH3:1]

参加物

5

反応物 2

HCID 784Hydrogen PeroxideHCID 666736235-[({1-[3-(1-Methylethyl)-1,2,4-oxadiazol-5-yl]-4-piperidinyl}methyl)oxy]-2-[4-(methylthio)phenyl]pyridine

生成物 1

HCID 46861617(+/-)-5-[({1-[3-(1-Methylethyl)-1,2,4-oxadiazol-5-yl]-4-piperidinyl}methyl)oxy]-2-[4-(methylsulfinyl)phenyl]pyridine収率 86%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 135291,1,1,3,3,3-Hexafluoro-2-propanol溶媒

反応条件

温度
8 °C

実験手順

A solution of 5-[({1-[3-(1-methylethyl)-1,2,4-oxadiazol-5-yl]-4-piperidinyl}methyl)oxy]-2-[4-(methylthio)phenyl]pyridine (93.7 g, 221 mol) in 1,1,1,3,3,3-hexafluoro-2-propanol (300 mL) at 5° C. was treated with 30% aqueous H2O2 (29 mL, 287 mol) over a 1.5 h period at such a rate to maintain temperature between approximately 6-10° C. The reaction was stirred at 5° C. for 2.5 h. The reaction was diluted with CH2Cl2 (600 mL), quenched by the addition of saturated aqueous Na2SO3 (400 mL), allowed to warm to room temperature and stirred for 30 min. The organic layer was washed with saturated aqueous Na2SO3 (400 mL×2), brine and was dried over MgSO4 and concentrated to give a tan solid. The solid was recrystallized from MeOH to provide the title compound (83.5 g, 86%) as a pale yellow solid. 1H NMR (400 MHz, CDCl3): δ 8.37 (d, 1H, J=2.7 Hz), 8.07 (d, 2H, J=8.4 Hz), 7.74-7.64 (m, 3H), 7.27 (dd, 1H, Ja=8.7 Hz, Jb=2.8 Hz), 4.30-4.15 (m, 2H), 3.92 (d, 2H, J=6.2 Hz), 3.20-3.05 (m, 2H), 2.87 (septet, 1H, J=6.9 Hz), 2.74 (s, 3H), 2.19-2.01 (m, 1H), 2.00-1.90 (m, 2H), 1.55-1.40 (m, 2H), 1.27 (d, 6H, J=7.0 Hz); LRMS (ESI), m/z 441 (M+H).

後処理

  1. customquenched by the addition of saturated aqueous Na2SO3 (400 mL)
  2. temperatureto warm to room temperature
  3. stirringstirred for 30 min
  4. washThe organic layer was washed with saturated aqueous Na2SO3 (400 mL×2), brine
  5. dry with materialwas dried over MgSO4
  6. concentrationconcentrated
  7. customto give a tan solid
  8. customThe solid was recrystallized from MeOH

出典と根拠

ORDレコード
ord-6c63daf8ec55434abe442dfe2588b863
出典データセット
uspto-grants-2012_01
特許番号
US08101634B2

反応ノート

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