Toluene → 4-(2,4-Dimethylphenyl)-[1,4]diazepane-1-carboxylic acid tert-butyl ester

HRID 2411223노트

반응식

HRID 2411223 반응식
Br[C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=1[CH3:9].[C:10]([N:17]1[CH2:23][CH2:22][CH2:21][NH:20][CH2:19][CH2:18]1)([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11].CC(C)([O-])C.[Na+].C1(C)C=CC=CC=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.O>[C:13]([O:12][C:10]([N:17]1[CH2:23][CH2:22][CH2:21][N:20]([C:2]2[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][C:3]=2[CH3:9])[CH2:19][CH2:18]1)=[O:11])([CH3:16])([CH3:14])[CH3:15]

참가 물질

8

반응물 4

HCID 1140TolueneHCID 68503Benzene, 1-bromo-2,4-dimethyl-HCID 2756058Tert-butyl 1,4-diazepane-1-carboxylateHCID 23676156Sodium t-butoxide

생성물 1

HCID 673808924-(2,4-Dimethylphenyl)-[1,4]diazepane-1-carboxylic acid tert-butyl ester수율 71.1%

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 634876Binap, (A+-)-촉매HCID 962Water용매

실험 절차

To a mixture of 1-bromo-2,4-dimethylbenzene (1.85 g), 1-Boc-[1,4]diazepane (2 g), palladium(II) acetate (0.12 g), rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (0.31 g) and sodium tert-butoxide (1.34 g) was added toluene (35 mL), and the mixture was stirred with heating under reflux for 9 hr. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine, and the solvent was evaporated. The obtained residue was purified by column chromatography (chloroform:methanol) to give 4-(2,4-dimethylphenyl)-[1,4]diazepane-1-carboxylic acid tert-butyl ester (2.16 g). The obtained 4-(2,4-dimethylphenyl)-[1,4]diazepane-1-carboxylic acid tert-butyl ester (2.16 g) was dissolved in chloroform (17 mL), 4N hydrogen chloride/ethyl acetate solution (6.9 mL) was added, and the mixture was stirred at room temperature overnight. The solvent was evaporated from the reaction mixture to give the title compound (1.74 g).

후처리

  1. temperaturewith heating
  2. temperatureunder reflux for 9 hr
  3. extractionthe mixture was extracted with ethyl acetate
  4. washThe organic layer was washed with saturated brine
  5. customthe solvent was evaporated
  6. customThe obtained residue was purified by column chromatography (chloroform:methanol)

출처 및 근거

ORD 기록
ord-f483749e08674f5295303218093b4dac
출처 데이터셋
uspto-grants-2014_08
특허 번호
US08816079B2

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