Benzoyl Peroxide → Tert-butyl [2-(4-bromo-benzoyl)-5-methoxy-benzyloxy]-carbamate

HRID 342220

反応式

HRID 342220 の反応式
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:10]2[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][C:11]=2[CH3:18])=[O:9])=[CH:4][CH:3]=1.CC1C=C(OC)C=CC=1.BrC1C=CC(C(Cl)=O)=CC=1.BrN1C(=O)CCC1=O.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1.[OH:64][NH:65][C:66](=[O:72])[O:67][C:68]([CH3:71])([CH3:70])[CH3:69].[H-].[Na+].[Cl-].[NH4+]>ClC(Cl)(Cl)Cl.C(Cl)Cl>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]([C:10]2[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][C:11]=2[CH2:18][O:64][NH:65][C:66](=[O:72])[O:67][C:68]([CH3:71])([CH3:70])[CH3:69])=[O:9])=[CH:6][CH:7]=1

参加物

11

反応物 8

HCID 7187Benzoyl PeroxideHCID 75303-MethoxytolueneHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 67184N-bromobutanimideHCID 685154-Bromobenzoyl chlorideHCID 97534tert-butyl N-hydroxycarbamateHCID 11023132(4-Bromophenyl)[2-methyl-4-(methyloxy)phenyl]methanone

生成物 1

HCID 10895395Tert-butyl [2-(4-bromo-benzoyl)-5-methoxy-benzyloxy]-carbamate収率 61.8%

試薬・触媒・溶媒 2

HCID 5943Carbon Tetrachloride溶媒HCID 6344Dichloromethane溶媒

実験手順

A solution of 3 g of (4-bromo-phenyl)-(2-methyl-4-methoxyphenyl)-methanone (prepared from 3-methylanisole and 4-bromobenzoyl chloride by Friedel-Crafts reaction analogously to Ex. 14a) in 100 ml of tetrachloromethane is treated with 2.1 g of N-bromosuccinimide and a spatula tip of dibenzoyl peroxide. The reaction mixture is stirred at room temperature for 6 hrs. under irradiation, subsequently diluted with 100 ml of methylene chloride and washed in succession with saturated sodium hydrogen carbonate solution and saturated sodium chloride solution. The organic phase is dried, filtered and immediately reacted. The solution is added dropwise to a mixture, previously stirred at 0° C., of 2.13 g of tert-butyl N-hydroxy-carbamate and 0.38 g of sodium hydride in 30 ml of TMF. The reaction mixture is warmed to room temperature and stirred. For the working-up, the mixture is treated with 60 ml of saturated ammonium chloride solution and the separated organic phase is washed with saturated sodium chloride solution, dried over sodium sulphate and concentrated. After chromatography of the residue (silica gel, ethyl acetate-hexane, 10:90 to 25:75) there are obtained 2.65 g of tert-butyl [2-(4-bromo-benzoyl)-5-methoxy-benzyloxy]-carbamate, MS: m/e 436 (M+H+, 1 Br).

後処理

  1. customunder irradiation
  2. washwashed in succession with saturated sodium hydrogen carbonate solution and saturated sodium chloride solution
  3. customThe organic phase is dried
  4. filtrationfiltered
  5. customimmediately reacted
  6. additionThe solution is added dropwise to a mixture
  7. temperatureThe reaction mixture is warmed to room temperature
  8. stirringstirred
  9. washthe separated organic phase is washed with saturated sodium chloride solution
  10. dry with materialdried over sodium sulphate
  11. concentrationconcentrated

出典と根拠

ORDレコード
ord-816aa45f140f4210b4cc54411f5fe371
出典データセット
uspto-grants-1999_01
特許番号
US05856503

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