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

HRID 27440

反応式

HRID 27440 の反応式
[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

参加物

12

反応物 4

HCID 7912DiisopropylamineHCID 693291-(Bromomethyl)-4-chlorobenzeneHCID 178418339ButyllithiumHCID 178418361HCID 178418361、化合物

生成物 1

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

試薬・触媒・溶媒 7

HCID 935Nickel触媒HCID 176Acetic Acid溶媒HCID 887Methanol溶媒HCID 3283Diethyl Ether溶媒HCID 6344Dichloromethane溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒

実験手順

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°.

後処理

  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

出典と根拠

ORDレコード
ord-cb458a2916c74c51ae19222b6a722a4f
出典データセット
uspto-grants-1980_09
特許番号
US04221788

関連ノート

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