Boron tribromide → [2-(4-Trifluoromethylphenyl)-6-hydroxybenzo[b]thien-3-yl][4-[2-(1-piperidinyl)ethoxy]phenyl]methanone

HRID 609823ノート

反応式

HRID 609823 の反応式
[F:1][C:2]([F:38])([F:37])[C:3]1[CH:8]=[CH:7][C:6]([C:9]2[S:13][C:12]3[CH:14]=[C:15]([O:18]C)[CH:16]=[CH:17][C:11]=3[C:10]=2[C:20]([C:22]2[CH:27]=[CH:26][C:25]([O:28][CH2:29][CH2:30][N:31]3[CH2:36][CH2:35][CH2:34][CH2:33][CH2:32]3)=[CH:24][CH:23]=2)=[O:21])=[CH:5][CH:4]=1.B(Br)(Br)Br>C(Cl)Cl.O>[F:38][C:2]([F:1])([F:37])[C:3]1[CH:4]=[CH:5][C:6]([C:9]2[S:13][C:12]3[CH:14]=[C:15]([OH:18])[CH:16]=[CH:17][C:11]=3[C:10]=2[C:20]([C:22]2[CH:27]=[CH:26][C:25]([O:28][CH2:29][CH2:30][N:31]3[CH2:32][CH2:33][CH2:34][CH2:35][CH2:36]3)=[CH:24][CH:23]=2)=[O:21])=[CH:7][CH:8]=1

参加物

5

反応物 2

HCID 25134Boron tribromide2 回HCID 10673987[2-(4-Trifluoromethylphenyl)-6-methoxybenzo[b]thien-3-yl][4-[2-(1-piperidinyl)ethoxy]phenyl]methanone

生成物 1

HCID 10744646[2-(4-Trifluoromethylphenyl)-6-hydroxybenzo[b]thien-3-yl][4-[2-(1-piperidinyl)ethoxy]phenyl]methanone収率 24%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-78 °C

実験手順

The product of Example 19 (480 mg, 0.89 mmol) was dissolved in anhydrous CH2Cl2 (15 mL), cooled to -78° C., and treated with a 1.0 M CH2Cl2 solution of boron tribromide (0.8 mL, 0.8 mmol). The mixture was allowed to warm to room temperature, stirred overnight, and treated with additional boron tribromide (1.75 mL, 1.75 mmol) in 2 portions. After 72 h, the mixture was diluted with 75 mL of water and extracted with CH2Cl2 (2×75 mL). The organic layers were washed with 2 N sodium hydroxide and the resultant aqueous layer was acidified and extracted with CH2Cl2 (75 mL). The combined organic layers were dried (Na2SO4), concentrated, and purified via radial chromatography (2:1:0.1 hexane:ethyl acetate:MeOH, under an ammonia atmosphere) to provide 110 mg (24%) of the title product as an amorphous green solid: 1H NMR d 1.45 (m, 2H), 1.63 (m, 4H), 2.57 (m, 4H), 2.79 (t, J=4.9 Hz, 2H), 4.08 (t, J=4.9 Hz, 2H), 6.59 (d, J=8.6 Hz, 2H), 6.77 (d, J=8.7 Hz, 1H), 7.15 (s, 1H), 7.33 (d, J=8.7 Hz, 1H), 7.42 (s, 4H), 7.64 (d, J=8.6 Hz, 2H), 8.18 (b, 1H); HRMS (FD+) m/e calc'd. for C29H27F3NO3S (MH+): 526.1664, found: 526.1669; Anal. calc'd for C29H26F3NO3S.H2O: C, 64.07; H, 5.20; N, 2.57. Found: C, 63.67; H, 5.12; N, 2.89.

後処理

  1. temperatureto warm to room temperature
  2. waitAfter 72 h
  3. extractionextracted with CH2Cl2 (2×75 mL)
  4. washThe organic layers were washed with 2 N sodium hydroxide
  5. extractionextracted with CH2Cl2 (75 mL)
  6. dry with materialThe combined organic layers were dried (Na2SO4)
  7. concentrationconcentrated
  8. custompurified via radial chromatography (2:1:0.1 hexane

出典と根拠

ORDレコード
ord-e9efe6884c424c7eacd1aae4b1d6d56d
出典データセット
uspto-grants-1999_12
特許番号
US05998442

反応ノート

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