1,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine) → HCID 58063370, 화합물

HRID 474348

반응식

HRID 474348 반응식
Cl[C:2]1[CH:7]=[CH:6][N:5]2[N:8]=[CH:9][C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:4]2[N:3]=1.[NH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[C:19]([C:23]([F:26])([F:25])[F:24])[N:18]=1.C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.CC(C)([O-])C.[Na+]>[Pd].[Pd].C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C(=CC(C=CC1C=CC=CC=1)=O)C1C=CC=CC=1.C1(C)C=CC=CC=1>[F:26][C:23]([F:24])([F:25])[C:19]1[N:18]=[C:17]([NH:16][C:2]2[CH:7]=[CH:6][N:5]3[N:8]=[CH:9][C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])=[C:4]3[N:3]=2)[CH:22]=[CH:21][CH:20]=1

참가 물질

7

반응물 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 8210242-Amino-6-(trifluoromethyl)pyridineHCID 23676156Sodium t-butoxideHCID 58063474Ethyl 5-chloropyrazolo(1,5-a)pyrimidine-3-carboxylate

생성물 1

HCID 58063370HCID 58063370, 화합물수율 17.3%

시약·촉매·용매 2

HCID 9832798Tris(dibenzylideneacetone) dipalladium촉매HCID 1140Toluene용매

반응 조건

온도
140 °C

실험 절차

A 20-mL microwave vial was charged with ethyl 5-chloropyrazolo[1,5-a]pyrimidine-3-carboxylate (1.28 g, 5.67 mmol, 1 equiv), 2-amino-6-(trifluoromethyl)pyridine (1.10 g, 6.81 mmol, 1.2 equiv), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (132 mg, 0.22 mmol, 4 mol %), tris(dibenzylideneacetone) dipalladium(0) (104 mg, 0.11 mmol, 2 mol %), sodium tert-butoxide (652 mg, 6.81 mmol, 1.2 equiv) and toluene (12 mL). The vial was sealed and the contents degassed, purged with argon and then heated in a microwave reactor at 140° C. for 20 minutes. After cooling, the mixture was diluted with ethyl acetate and filtered through a pad of Celite®. The filtrate was washed with water and saturated aqueous sodium chloride solution, dried over anydrous sodium sulphate, filtered, and concentrated under vacuum. The resultant residue was purified by flash column chromatography on silica gel (gradient: 0 to 20% ethyl acetate in dichloromethane) to give 344 mg (17%) of ethyl 5-(6-(trifluoromethyl)pyridin-2-ylamino)pyrazolo[1,5-a]pyrimidine-3-carboxylate as an orange solid. LCMS (ESI) m+H=352.1; 1H NMR (300 MHz, DMSO-d6) δ: 11.06 (s, 1H), 9.16 (d, 1H), 8.94 (d, 1H), 8.39 (s, 1H), 8.10 (t, 1H), 7.57 (d, 1H), 7.05 (d, 1H), 4.31 (q, 2H), 1.40 (t, 3H).

후처리

  1. customThe vial was sealed
  2. customthe contents degassed
  3. custompurged with argon
  4. temperatureAfter cooling
  5. additionthe mixture was diluted with ethyl acetate
  6. filtrationfiltered through a pad of Celite®
  7. washThe filtrate was washed with water and saturated aqueous sodium chloride solution
  8. dry with materialdried over anydrous sodium sulphate
  9. filtrationfiltered
  10. concentrationconcentrated under vacuum
  11. customThe resultant residue was purified by flash column chromatography on silica gel (gradient: 0 to 20% ethyl acetate in dichloromethane)

출처 및 근거

ORD 기록
ord-8a871980f923411c83f3a5de483d0e73
출처 데이터셋
uspto-grants-2014_01
특허 번호
US08637526B2

연결된 노트

불러오는 중…