Water → (Z)-7-chloro-3-(2-chlorobenzyl)-5-(4-hydroxyphenyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one

HRID 885014ノート

反応式

HRID 885014 の反応式
[Cl:1][C:2]1[CH:30]=[CH:29][C:5]2[N:6]([CH3:28])[C:7](=[O:27])[CH:8]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[Cl:26])[N:9]=[C:10]([C:11]3[CH:16]=[CH:15][C:14]([O:17]C)=[CH:13][CH:12]=3)[C:4]=2[CH:3]=1.B(Br)(Br)Br.O>C(Cl)Cl.[Cl-].[Na+].O>[Cl:1][C:2]1[CH:30]=[CH:29][C:5]2[N:6]([CH3:28])[C:7](=[O:27])[CH:8]([CH2:19][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][C:21]=3[Cl:26])[N:9]=[C:10]([C:11]3[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=3)[C:4]=2[CH:3]=1

参加物

6

反応物 3

HCID 962WaterHCID 25134Boron tribromide2 回HCID 59594376HCID 59594376、化合物

生成物 1

HCID 135869723(Z)-7-chloro-3-(2-chlorobenzyl)-5-(4-hydroxyphenyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one収率 8.1%

試薬・触媒・溶媒 2

HCID 6344Dichloromethane溶媒HCID 57417360Sodium chloride; water溶媒

反応条件

温度
-78 °C

実験手順

(Z)-7-chloro-3-(2-chlorobenzyl)-5-(4-methoxyphenyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one (230 mg, 0.524 mmol) was dissolved in methylene chloride (5 mL) and cooled to −78° C. under nitrogen. Boron tribromide (54 μL 0.576 mmol) was added dropwise. The mixture turned orange. It was kept at −78° C. for 2 h then allowed to warm to RT. Tlc indicated no reaction after 6 hr. An additional equivalent of boron tribromide was added. The mixture was left stirring overnight at RT. Carefully added water (2 mL) then brine (2 mL). The aqueous layer was extracted twice with methylene chloride. The combined organic layers were dried over magnesium sulfate then filtered and the solvent evaporated. The residue was chromatographed on silica gel eluting with 30-50% ethyl acetate in hexanes to give (Z)-7-chloro-3-(2-chlorobenzyl)-5-(4-hydroxyphenyl)-1-methyl-1H-benzo[e][1,4]diazepin-2(3H)-one as a yellow solid (18 mg). 1H NMR (300 MHz, CDCl3) δ 3.4 (s, 3H), 3.6-3.8 (m, 2H), 3.8-3.9 (m, 1H), 6.8 (d, 2H), 7.1-7.6 (m, 9H); ESI m/z measured 425.0828 [M+H+], calculated 425.0824.

後処理

  1. temperatureto warm to RT
  2. customno reaction after 6 hr
  3. waitThe mixture was left
  4. extractionThe aqueous layer was extracted twice with methylene chloride
  5. dry with materialThe combined organic layers were dried over magnesium sulfate
  6. filtrationthen filtered
  7. customthe solvent evaporated
  8. customThe residue was chromatographed on silica gel eluting with 30-50% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-7b4805385fd24cf7aa853f43de54e959
出典データセット
uspto-grants-2012_08
特許番号
US08242109B2

反応ノート

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