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1,4-Dioxane → 6-{4-[(dimethylamino)methyl]phenyl}-1-(1-methylethyl)-N-[(6-methyl-2-oxo-4-propyl-1,2-dihydro-3-pyridinyl)methyl]-1H-indazole-4-carboxamide hydrochloride salt

HRID 85443
Notizen
Druckvorschau

Reaktionsgleichung

Reaktionsgleichung von HRID 85443
Br[C:2]1[CH:3]=[C:4]([C:14]([NH:16][CH2:17][C:18]2[C:19](=[O:28])[NH:20][C:21]([CH3:27])=[CH:22][C:23]=2[CH2:24][CH2:25][CH3:26])=[O:15])[C:5]2[CH:6]=[N:7][N:8]([CH:11]([CH3:13])[CH3:12])[C:9]=2[CH:10]=1.[ClH:29].[CH3:30][N:31]([CH2:33][C:34]1[CH:39]=[CH:38][C:37](B2OC(C)(C)C(C)(C)O2)=[CH:36][CH:35]=1)[CH3:32].P([O-])([O-])([O-])=O.[K+].[K+].[K+].O1CCOCC1>C(Cl)Cl.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(Cl)Cl.O>[ClH:29].[CH3:30][N:31]([CH2:33][C:34]1[CH:39]=[CH:38][C:37]([C:2]2[CH:3]=[C:4]([C:14]([NH:16][CH2:17][C:18]3[C:19](=[O:28])[NH:20][C:21]([CH3:27])=[CH:22][C:23]=3[CH2:24][CH2:25][CH3:26])=[O:15])[C:5]3[CH:6]=[N:7][N:8]([CH:11]([CH3:13])[CH3:12])[C:9]=3[CH:10]=2)=[CH:36][CH:35]=1)[CH3:32]
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Komponenten

8

Edukt 4

HCID 312751,4-DioxaneHCID 62657Potassium Phosphate, TribasicHCID 44118821Dimethyl({[4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]methyl})amine hydrochlorideHCID 674653266-bromo-1-(1-methylethyl)-N-[(6-methyl-2-oxo-4-propyl-1,2-dihydro-3-pyridinyl)methyl]-1H-indazole-4-carboxamide

Produkt 1

HCID 54596917
6-{4-[(dimethylamino)methyl]phenyl}-1-(1-methylethyl)-N-[(6-methyl-2-oxo-4-propyl-1,2-dihydro-3-pyridinyl)methyl]-1H-indazole-4-carboxamide hydrochloride salt
Ausbeute 85,2 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 178418807HCID 178418807, VerbindungKatalysatorHCID 962WaterLösungsmittelHCID 6344DichloromethaneLösungsmittel

Versuchsvorschrift

In a glass pressure tube was added 6-bromo-1-(1-methylethyl)-N-[(6-methyl-2-oxo-4-propyl-1,2-dihydro-3-pyridinyl)methyl]-1H-indazole-4-carboxamide (200 mg, 0.449 mmol), 4-(N,N-dimethylaminomethyl)phenylboronic acid pinacol ester hydrochloride (170 mg, 0.571 mmol), potassium phosphate (300 mg, 1.413 mmol), dioxane (12 mL) and water (3 mL). The suspension was stirred and purged with N2 then PdCl2(dppf)-CH2Cl2 adduct (50 mg, 0.061 mmol) was added. The reaction mixture was capped and stirred at 110° C. for 4 hr. The dark black reaction mixture was evaporated to dryness. The crude product was purified by silica gel chromatography (eluent: 0 to 70%, 20% (5% NH4OH in MeOH)/CH2Cl2) in CH2Cl2). The pure fractions were combined and evaporated to dryness to give the product as a very dark brown-black solid. The solid was taken up in CH2Cl2 and treated with Silicycle Si-Thiol (2 g, 1.46 mMol/g). After stirring for 30 minutes on a rotary evaporator (no vacuum) the mixture was filtered through a pad of Celite, washed with CH2Cl2, and evaporated to dryness. The light yellow colored solid was taken up in a small volume of MeOH and treated with 6 N HCl (200 uL) and re-evaporated to dryness. The residue was dissolved in a small volume of MeOH, ppt. with Et2O, triturated, filtered and dried under vacuum to give the product 6-{4-[(dimethylamino)methyl]phenyl}-1-(1-methylethyl)-N-[(6-methyl-2-oxo-4-propyl-1,2-dihydro-3-pyridinyl)methyl]-1H-indazole-4-carboxamide hydrochloride salt as a light tan solid (205 mg, 85% yield). 1H NMR (400 MHz, DMSO-d6) δ=11.60 (br. s., 1H), 10.81 (br. s., 1H), 8.69 (t, J=4.9 Hz, 1H), 8.40 (s, 1H), 8.19 (s, 1H), 7.97 (d, J=8.3 Hz, 2H), 7.90 (d, J=1.0 Hz, 1H), 7.71 (d, J=8.3 Hz, 2H), 5.94 (s, 1H), 5.18 (dt, J=6.7, 13.2 Hz, 1H), 4.43 (d, J=4.8 Hz, 2H), 4.34 (d, J=5.3 Hz, 2H), 2.72 (d, J=5.1 Hz, 6H), 2.58-2.52 (m, 2H), 2.14 (s, 3H), 1.59-1.52 (m, 2H), 1.51 (d, J=6.6 Hz, 6H), 0.89 (t, J=7.3 Hz, 3H); LC-MS(ES)+ m/e 500.2 [M+H]+.

Aufarbeitung

  1. custompurged with N2
  2. customThe reaction mixture was capped
  3. stirringstirred at 110° C. for 4 hr
  4. customThe dark black reaction mixture
  5. customwas evaporated to dryness
  6. customThe crude product was purified by silica gel chromatography (eluent: 0 to 70%, 20% (5% NH4OH in MeOH)/CH2Cl2) in CH2Cl2)
  7. customevaporated to dryness
  8. customto give the product as a very dark brown-black solid
  9. stirringAfter stirring for 30 minutes on a rotary evaporator (no vacuum) the mixture
  10. filtrationwas filtered through a pad of Celite
  11. washwashed with CH2Cl2
  12. customevaporated to dryness
  13. additiontreated with 6 N HCl (200 uL)
  14. customre-evaporated to dryness
  15. dissolutionThe residue was dissolved in a small volume of MeOH, ppt
  16. customwith Et2O, triturated
  17. filtrationfiltered
  18. customdried under vacuum

Quellen und Nachweise

ORD-Eintrag
ord-cf21743fe0784ebdb4b010cfeef186af
Quelldatensatz
uspto-grants-2014_09
DOI
10.6084/m9.figshare.5104873.v1
Patentnummer
US08846935B2

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