Binap, (A+-)- → tert-Butyl 2-(6-bromopyridin-3-ylamino)-5-methylbenzoate

HRID 42003노트

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HRID 42003 반응식
[NH2:1][C:2]1[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5].[Br:16][C:17]1[CH:22]=[CH:21][C:20](I)=[CH:19][N:18]=1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC([O-])(C)C.[Na+]>C1(C)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].C(OCC)(=O)C.O>[Br:16][C:17]1[N:18]=[CH:19][C:20]([NH:1][C:2]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][C:3]=2[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])=[CH:21][CH:22]=1

참가 물질

9

반응물 4

HCID 634876Binap, (A+-)-HCID 47382712-Bromo-5-iodopyridineHCID 13399998tert-Butyl 2-amino-5-methylbenzoateHCID 23676156Sodium t-butoxide

생성물 1

HCID 86657255tert-Butyl 2-(6-bromopyridin-3-ylamino)-5-methylbenzoate수율 40.2%

시약·촉매·용매 4

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 962Water용매HCID 1140Toluene용매HCID 8857Ethyl Acetate용매

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온도
120 °C

실험 절차

In a schlenck tube, a mixture of tert-butyl 2-amino-5-methylbenzoate (2.89 mmol, 0.600 g), 2-bromo-5-iodopyridine (2.89 mmol, 0.822 g), BINAP (0.29 mmol, 0.096 g), Pd2(dba)3 (0.14 mmol, 0.132 g) and NaOtBu (5.79 mmol, 0.556 g) in toluene (15 ml) was heated at 120° C. for 3 hours. Water and ethyl acetate were added to the reaction crude. The aqueous phase was extracted again with more ethyl acetate. The organic phase was washed with water and brine, dried, filtered and concentrated in vacuo. The crude mixture was purified by chromatography (Biotage 40S, SiO2, Hexane:Ethyl acetate from 0% to 10%) affording 0.422 g (yield 40%) of the expected product.

후처리

  1. extractionThe aqueous phase was extracted again with more ethyl acetate
  2. washThe organic phase was washed with water and brine
  3. customdried
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude mixture was purified by chromatography (Biotage 40S, SiO2, Hexane:Ethyl acetate from 0% to 10%)

출처 및 근거

ORD 기록
ord-526c59565f6c4553ab53563a4218665a
출처 데이터셋
uspto-grants-2013_09
특허 번호
US08536165B2

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