Binap, (A+-)- → Ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate

HRID 446314

반응식

HRID 446314 반응식
Cl[C:2]1[C:7]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][N:9]=2)=[CH:6][CH:5]=[CH:4][N:3]=1.[NH2:14][C:15]1[CH:16]=[C:17]([CH:23]=[CH:24][C:25]=1[C:26]([F:29])([F:28])[F:27])[C:18]([O:20][CH2:21][CH3:22])=[O:19].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>C1(C)C=CC=CC=1.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N:11]1[CH:12]=[CH:13][C:8]([C:7]2[C:2]([NH:14][C:15]3[CH:16]=[C:17]([CH:23]=[CH:24][C:25]=3[C:26]([F:27])([F:28])[F:29])[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[N:3][CH:4]=[CH:5][CH:6]=2)=[N:9][CH:10]=1

참가 물질

8

반응물 4

HCID 634876Binap, (A+-)-HCID 161089744-(2-Chloropyridin-3-yl)pyrimidineHCID 19783159Ethyl 3-amino-4-(trifluoromethyl)benzoateHCID 23676156Sodium t-butoxide

생성물 1

HCID 66970285Ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 1140Toluene용매HCID 8857Ethyl Acetate용매

반응 조건

온도
80 °C

실험 절차

4-(2-Chloropyridin-3-yl)pyrimidine (1.5 g, 7.8 mmol), ethyl 3-amino-4-(trifluoromethyl)benzoate (2.0 g, 8.6 mmol), Sodium tert-butoxide (1.1 g, 12 mmol), rac-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (0.49 g, 0.78 mmol) were all mixed together in toluene (25 ml) and degassed under vacuum. Nitrogen was bubbled into the reaction for 5 minutes and then Palladium (II) acetate (0.088 g, 0.39 mmol) was added. The mixture was heated to 80° C. and stirred overnight. The reaction was diluted with ethyl acetate and washed with an aqueous saturated solution of sodium bicarbonate, water and brine. The organic layer was then dried with sodium sulfate and purified by column chromatography on silica gel using a gradient 5 to 40% ethyl acetate in hexanes to afford ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate as a brown solid. MS m/z=389 [M+1]+. Calc'd for C19H15F3N4O2: 388.11.

후처리

  1. customdegassed under vacuum
  2. customNitrogen was bubbled into the reaction for 5 minutes
  3. washwashed with an aqueous saturated solution of sodium bicarbonate, water and brine
  4. dry with materialThe organic layer was then dried with sodium sulfate
  5. custompurified by column chromatography on silica gel using a gradient 5 to 40% ethyl acetate in hexanes

출처 및 근거

ORD 기록
ord-f176647a0d194514a51ae28998697137
출처 데이터셋
uspto-grants-2013_07
특허 번호
US08476434B2

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