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Cesium carbonate → 5-Cyano-3-methyl-pyridine-2-carboxylic acid [4-(5-amino-6,6-bis-fluoromethyl-3-methyl-3,6-dihydro-2H-[1,4]oxazin-3-yl)-5-fluoro-pyridin-2-yl]-amide

HRID 538373
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 538373
[C:1]([C:3]1[CH:4]=[C:5]([CH3:12])[C:6]([C:9]([NH2:11])=[O:10])=[N:7][CH:8]=1)#[N:2].Br[C:14]1[CH:19]=[C:18]([C:20]2([CH3:31])[CH2:25][O:24][C:23]([CH2:28][F:29])([CH2:26][F:27])[C:22]([NH2:30])=[N:21]2)[C:17]([F:32])=[CH:16][N:15]=1.CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.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]>[NH2:30][C:22]1[C:23]([CH2:26][F:27])([CH2:28][F:29])[O:24][CH2:25][C:20]([C:18]2[C:17]([F:32])=[CH:16][N:15]=[C:14]([NH:11][C:9]([C:6]3[C:5]([CH3:12])=[CH:4][C:3]([C:1]#[N:2])=[CH:8][N:7]=3)=[O:10])[CH:19]=2)([CH3:31])[N:21]=1
KomponentenReaktionsbedingungenVersuchsvorschriftAufarbeitungQuellen und NachweiseNotizen zur Reaktion

Komponenten

7

Edukt 4

HCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)2×HCID 666659355-Cyano-3-methyl-2-pyridinecarboxamideHCID 866680815-(2-Bromo-5-fluoro-pyridin-4-yl)-2,2-bis-fluoromethyl-5-methyl-5,6-dihydro-2H-[1,4]oxazin-3-ylamine

Produkt 1

HCID 77831077
5-Cyano-3-methyl-pyridine-2-carboxylic acid [4-(5-amino-6,6-bis-fluoromethyl-3-methyl-3,6-dihydro-2H-[1,4]oxazin-3-yl)-5-fluoro-pyridin-2-yl]-amide

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysator2×HCID 312751,4-DioxaneLösungsmittel

Reaktionsbedingungen

Temperatur
60 °C

Versuchsvorschrift

A mixture of 5-cyano-3-methyl-pyridine-2-carboxylic acid amide (see Intermediates Amide 1, 96 mg, 0.596 mmol), 5-(2-bromo-5-fluoro-pyridin-4-yl)-2,2-bis-fluoromethyl-5-methyl-5,6-dihydro-2H-[1,4]oxazin-3-ylamine (210 mg, 0.596 mmol), Xantphos (31.1 mg, 0.054 mmol) and Cs2CO3 (272 mg, 0.835 mmol) in dioxane (6 ml) was degassed with argon, Pd2(dba)3 (16.38 mg, 0.018 mmol) was added and the reaction mixture was stirred at 60° C. for 16 h. More Pd2(dba)3 (8.19 mg, 0.009 mmol) and Xantphos (15.60 mg, 0.027 mmol) was added and stirring was continued at 60° C. for 4 h. The reaction mixture was filtered through celite and the celite pad rinsed with DCM. The combined filtrates were concentrated and the resulting crude title compound was purified by NP-HPLC (Alltech Grom Saphir65 Si 10 μm column, 150×30 mm, gradient n-heptane:EtOAc:MeOH 68:30:2 to 0:65:35), then by RP-HPLC (Waters SunFire C18 column, 5 μM, 30×100 mm, gradient 10 to 30% ACN+0.1% TFA) and obtained as a free base after filtration over an SCX cartridge.

Aufarbeitung

  1. additionwas added
  2. stirringstirring
  3. waitwas continued at 60° C. for 4 h
  4. filtrationThe reaction mixture was filtered through celite
  5. washthe celite pad rinsed with DCM
  6. concentrationThe combined filtrates were concentrated
  7. customthe resulting crude title compound was purified by NP-HPLC (Alltech Grom Saphir65 Si 10 μm column, 150×30 mm, gradient n-heptane:EtOAc:MeOH 68:30:2 to 0:65:35), then by RP-HPLC (Waters SunFire C18 column, 5 μM, 30×100 mm, gradient 10 to 30% ACN+0.1% TFA)
  8. customobtained as a free base
  9. filtrationafter filtration over an SCX cartridge

Quellen und Nachweise

ORD-Eintrag
ord-ecea7acdb5004c8c8cc31744a4e7737d
Quelldatensatz
uspto-grants-2014_10
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08865712B2

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