Diisopropylamine → 2-[(4-Chlorophenyl)methyl]azepane

HRID 27440

반응식

HRID 27440 반응식
[CH2:1]([Li])[CH2:2]CC.[CH:6]([NH:9][CH:10]([CH3:12])[CH3:11])([CH3:8])C.[Cl:13][C:14]1[CH:21]=[CH:20][C:17](CBr)=[CH:16][CH:15]=1.[H][H]>CCCCCC.O1CCCC1.CO.[Ni].ClCCl.C(O)(=O)C.C(OCC)C>[Cl:13][C:14]1[CH:15]=[CH:16][C:17]([CH2:12][CH:10]2[CH2:11][CH2:2][CH2:1][CH2:8][CH2:6][NH:9]2)=[CH:20][CH:21]=1

참가 물질

12

반응물 4

HCID 7912DiisopropylamineHCID 693291-(Bromomethyl)-4-chlorobenzeneHCID 178418339ButyllithiumHCID 178418361HCID 178418361, 화합물

생성물 1

HCID 39338092-[(4-Chlorophenyl)methyl]azepane

시약·촉매·용매 7

HCID 935Nickel촉매HCID 176Acetic Acid용매HCID 887Methanol용매HCID 3283Diethyl Ether용매HCID 6344Dichloromethane용매HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매

실험 절차

Add a solution of 10 mmol of n-butyllithium in n-hexane to a solution of 1.01 g of diisopropylamine in 100 ml of tetrahydrofuran at 78° and pass argon through it. Stir the mixture for 5 minutes at room temperature and then cool it down again to -78°. Add a solution of 1.28 g of n-nitrosoperhydroazepine and stir for 1 hour. Then add 4.1 g of 4-chlorobenzyl bromide in a small amount of diethyl ether. After stirring for another 5 hours at -78° add 5 ml of glacial acetic acid. Warm the mixture up to room temperature and pour it into 100 ml of dichloromethane-saturated sodium chloride solution. Free the organic phase from the solvent and then solve it in methanol. After addition of 2 g of freshly prepared Laney nickel, pass hydrogen through the solution while stirring vigorously. Filter off the catalyst, and wash the catalyst with methanol. Concentrate the methanolic filtrate. Treat the oily residue with ethanol-ethereal hydrochloric acid to obtain the hydrochloride of the title compound: m.p. 176° to 178°.

후처리

  1. temperaturecool it down again to -78°
  2. stirringstir for 1 hour
  3. stirringAfter stirring for another 5 hours at -78°
  4. temperatureWarm the mixture up to room temperature
  5. stirringwhile stirring vigorously
  6. filtrationFilter off the catalyst
  7. washwash the catalyst with methanol
  8. concentrationConcentrate the methanolic filtrate
  9. additionTreat the oily residue with ethanol-ethereal hydrochloric acid

출처 및 근거

ORD 기록
ord-cb458a2916c74c51ae19222b6a722a4f
출처 데이터셋
uspto-grants-1980_09
특허 번호
US04221788

연결된 노트

불러오는 중…