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llms.txt · MCP 가이드개인정보처리방침 · 이용약관 · 지원v1.8.0
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Ammonium Chloride → 8-(2,4-Difluorophenoxy)-7-(6-methyl-7-oxo-1-{[2-(trimethylsilyl)ethoxy]methyl}-6,7-dihydro-1H-pyrazolo[3,4-c]pyridin-4-yl)-3,4-dihydroquinoxalin-2(1H)-one

HRID 1056978
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HRID 1056978 반응식
[F:1][C:2]1[CH:42]=[C:41]([F:43])[CH:40]=[CH:39][C:3]=1[O:4][C:5]1[C:6]([N+:36]([O-])=O)=[C:7]([NH:30][CH2:31][C:32](OC)=[O:33])[CH:8]=[CH:9][C:10]=1[C:11]1[C:12]2[CH:21]=[N:20][N:19]([CH2:22][O:23][CH2:24][CH2:25][Si:26]([CH3:29])([CH3:28])[CH3:27])[C:13]=2[C:14](=[O:18])[N:15]([CH3:17])[CH:16]=1.[Cl-].[NH4+]>C(OCC)(=O)C.CO.ClCCl.[Zn]>[F:1][C:2]1[CH:42]=[C:41]([F:43])[CH:40]=[CH:39][C:3]=1[O:4][C:5]1[C:10]([C:11]2[C:12]3[CH:21]=[N:20][N:19]([CH2:22][O:23][CH2:24][CH2:25][Si:26]([CH3:29])([CH3:28])[CH3:27])[C:13]=3[C:14](=[O:18])[N:15]([CH3:17])[CH:16]=2)=[CH:9][CH:8]=[C:7]2[C:6]=1[NH:36][C:32](=[O:33])[CH2:31][NH:30]2
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참가 물질

7

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HCID 25517Ammonium ChlorideHCID 131736451Methyl {[3-(2,4-difluorophenoxy)-4-(6-methyl-7-oxo-1-{[2-(trimethylsilyl)ethoxy]methyl}-6,7-dihydro-1H-pyrazolo[3,4-c]pyridin-4-yl)-2-nitrophenyl]amino}acetate

생성물 1

HCID 1232172868-(2,4-Difluorophenoxy)-7-(6-methyl-7-oxo-1-{[2-(trimethylsilyl)ethoxy]methyl}-6,7-dihydro-1H-pyrazolo[3,4-c]pyridin-4-yl)-3,4-dihydroquinoxalin-2(1H)-one수율 24.3%

시약·촉매·용매 4

HCID 23994
Zinc
촉매
HCID 887Methanol용매
HCID 6344Dichloromethane용매2회
HCID 8857Ethyl Acetate용매

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온도
0 °C

실험 절차

A suspension of methyl {[3-(2,4-difluorophenoxy)-4-(6-methyl-7-oxo-1-{[2-(trimethylsilyl)ethoxy]methyl}-6,7-dihydro-1H-pyrazolo[3,4-c]pyridin-4-yl)-2-nitrophenyl]amino}acetate (0.048 g, 0.078 mmol) in ethyl acetate (0.452 mL) and methanol (0.452 mL) was cooled to 0° C. and then treated with saturated ammonium chloride solution (0.0679 mL, 1.01 mmol) at that temperature. Zinc (0.0408 g, 0.624 mmol) was added to the reaction mixture in two portions over 5 min and the reaction mixture was stirred at RT for 16 h. The reaction mixture was diluted with dichloromethane and filtered through a pad of Celite. The solids were washed with additional dichloromethane and the filtrate was concentrated in vacuo to yield a crude residue. The residue was dissolved in dichloromethane and the organic phase was washed with saturated sodium bicarbonate solution, dried with sodium sulfate, filtered, and concentrated in vacuo to give the crude product. Purification via preparative LCMS (XBridge C18 column, eluting with a gradient of acetonitrile/water 0.1% ammonium hydroxide, at flow rate of 60 mL/min) gave the desired product (10.5 mg, 24%) along with a small amount of the oxidized product, 8-(2,4-difluorophenoxy)-7-(6-methyl-7-oxo-1-{[2-(trimethylsilyl)ethoxy]methyl}-6,7-dihydro-1H-pyrazolo[3,4-c]pyridin-4-yl)quinoxalin-2(1H)-one. This mixture was used in the next step without separation. LCMS calculated for C27H30F2N5O4Si (M+H)+: m/z=554.2. found: 554.1.

후처리

  1. filtrationfiltered through a pad of Celite
  2. washThe solids were washed with additional dichloromethane
  3. concentrationthe filtrate was concentrated in vacuo
  4. customto yield a crude residue
  5. washthe organic phase was washed with saturated sodium bicarbonate solution
  6. dry with materialdried with sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give the crude product
  10. customPurification via preparative LCMS (XBridge C18 column
  11. washeluting with a gradient of acetonitrile/water 0.1% ammonium hydroxide, at flow rate of 60 mL/min)

출처 및 근거

ORD 기록
ord-a6bbd9fb381747e2b0e6cbbbce35fcbe
출처 데이터셋
uspto-grants-2016_07
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US09399640B2

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