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Nitrogen → 7-(1-Ethyl-propyl)-3-(2,4-dichloro-thiazol-5-yl)-2,5-dimethyl-pyrazolo[1,5-a]pyrimidine

HRID 1044662
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HRID 1044662 반응식
[CH2:1]([CH:3]([C:6]1[N:11]2[N:12]=[C:13]([CH3:16])[C:14](I)=[C:10]2[N:9]=[C:8]([CH3:17])[CH:7]=1)[CH2:4][CH3:5])[CH3:2].[O-]P([O-])([O-])=O.[K+].[K+].[K+].[Cl:26][C:27]1[S:28][CH:29]=[C:30]([Cl:32])[N:31]=1.N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.N#N>[Cu]I.CC(N(C)C)=O>[CH2:1]([CH:3]([C:6]1[N:11]2[N:12]=[C:13]([CH3:16])[C:14]([C:29]3[S:28][C:27]([Cl:26])=[N:31][C:30]=3[Cl:32])=[C:10]2[N:9]=[C:8]([CH3:17])[CH:7]=1)[CH2:4][CH3:5])[CH3:2]
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참가 물질

8

반응물 5

HCID 947NitrogenHCID 13181,10-PhenanthrolineHCID 62657Potassium Phosphate, TribasicHCID 123331552,4-DichlorothiazoleHCID 248985233-Iodo-2,5-dimethyl-7-(pentan-3-yl)pyrazolo[1,5-a]pyrimidine

생성물 1

HCID 452757037-(1-Ethyl-propyl)-3-(2,4-dichloro-thiazol-5-yl)-2,5-dimethyl-pyrazolo[1,5-a]pyrimidine
수율 70%

시약·촉매·용매 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 31374Dimethylacetamide용매

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온도
120 °C

실험 절차

Charge 7-(1-ethyl-propyl)-3-iodo-2,5-dimethyl-pyrazolo[1,5-a]pyrimidine (1.03 g, 3.00 mmoles), K3PO4 (1.95 g, 9.00 mmoles), 2,4-dichlorothiazole (0.58 g, 3.75 mmoles), 1,10 phenanthroline (0.05 g, 0.30 mmoles) and anhydrous DMAC (5 mL) to a round bottom flask equipped with a magnetic stir bar, thermal couple and N2 inlet. Degas the yellow heterogeneous reaction mixture with N2 (gas) for 30 min. and then add CuI (0.06 g, 0.30 mmoles) in one portion followed by additional 30 min. degassing with N2 (gas). Stir the reaction mixture at 120° C. for about 6 hr. Cool the reaction mixture to room temperature overnight, add toluene (10 mL) and stir for 1 hr. Purify the mixture through silica gel eluting with toluene (10 ml). Extract with 1 M HCl (10 mL), water (10 mL), brine (10 mL) and concentrate under reduced pressure to give a yellow solid. Recrystallize the solid from methanol (5 ml) to yield the title compound as a yellow crystalline solid. (0.78 g, 70% yield, >99% pure by LC) MS (ES)=369 (M+1). 1H NMR (CDCl3)=6.5 (1H, s); 3.6 (1H, m); 2.6 (3H, s); 2.5 (3H, s); 1.9 (4H, m); 0.9 (6H, t).

후처리

  1. customequipped with a magnetic stir bar
  2. customDegas the yellow heterogeneous reaction mixture with N2 (gas) for 30 min.
  3. customdegassing with N2 (gas)
  4. temperatureCool the reaction mixture to room temperature overnight
  5. additionadd toluene (10 mL)
  6. stirringstir for 1 hr
  7. customPurify the mixture through silica gel eluting with toluene (10 ml)
  8. extractionExtract with 1 M HCl (10 mL), water (10 mL), brine (10 mL)
  9. concentrationconcentrate under reduced pressure
  10. customto give a yellow solid
  11. customRecrystallize the solid from methanol (5 ml)

출처 및 근거

ORD 기록
ord-e81da3655835453dae1e8e6d9352def3
출처 데이터셋
uspto-grants-2013_10
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US08563718B2

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