Benzylamine → tert-Butyl 1-[3-(benzylamino)-4-chlorobenzyl]cyclopropanecarboxylate

HRID 626417노트

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HRID 626417 반응식
Br[C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][C:18]=1[Cl:19])[CH2:5][C:6]1([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:8][CH2:7]1.[CH2:20]([NH2:27])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.CC(C)([O-])C.[Na+].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>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(C)C=CC=CC=1>[CH2:20]([NH:27][C:2]1[CH:3]=[C:4]([CH:16]=[CH:17][C:18]=1[Cl:19])[CH2:5][C:6]1([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:8][CH2:7]1)[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

참가 물질

7

반응물 4

HCID 7504BenzylamineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 67958496tert-Butyl 1-(3-bromo-4-chlorobenzyl)cyclopropanecarboxylate

생성물 1

HCID 68006927tert-Butyl 1-[3-(benzylamino)-4-chlorobenzyl]cyclopropanecarboxylate

시약·촉매·용매 2

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 1140Toluene용매

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온도
110 °C

실험 절차

Under argon, 95.0 g (274.8 mmol) of tert-butyl 1-(3-bromo-4-chlorobenzyl)cyclopropanecarboxylate, 36.0 ml (330.0 mmol) of benzylamine, 12.58 g (13.7 mmol) of tris(dibenzylideneacetone)dipalladium, 31.69 g (329.8 mmol) of sodium tert-butoxide and 6.85 g (5.29 mmol) of (+/−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl were added successively to 633 ml of dry toluene. The reaction mixture was stirred at 110° C. for 3.0 h and then at RT overnight. The reaction mixture was then filtered off with suction through kieselguhr and the residue was washed thoroughly with toluene and ethyl acetate. The combined filtrates were concentrated under reduced pressure. The crude product was purified by chromatography on silica gel (mobile phase petroleum ether/ethyl acetate 10:1). This gave 50.0 g of the title compound (48.9% of theory).

후처리

  1. customat RT
  2. customovernight
  3. filtrationThe reaction mixture was then filtered off with suction through kieselguhr
  4. washthe residue was washed thoroughly with toluene and ethyl acetate
  5. concentrationThe combined filtrates were concentrated under reduced pressure
  6. customThe crude product was purified by chromatography on silica gel (mobile phase petroleum ether/ethyl acetate 10:1)

출처 및 근거

ORD 기록
ord-3ea8b786da7843b7b1e868f076eea165
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09309198B2

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