Hydrochloric Acid → N-(2-bromo-4-(1-methylethyl)phenyl)-N-ethyl-4-(1-aminoethyl)-6-methylpyrimidinamine

HRID 1872059Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1872059
[Br:1][C:2]1[CH:7]=[C:6]([CH:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][C:3]=1[N:11]([CH2:22][CH3:23])[C:12]1[N:17]=[C:16]([C:18](=[O:20])[CH3:19])[CH:15]=[C:14]([CH3:21])[N:13]=1.C([O-])(=O)C.[NH4+].C([BH3-])#[N:30].[Na+].Cl>C(OCC)(=O)C.CO.C(Cl)(Cl)Cl>[NH4+:11].[OH-:20].[Br:1][C:2]1[CH:7]=[C:6]([CH:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][C:3]=1[N:11]([CH2:22][CH3:23])[C:12]1[N:17]=[C:16]([CH:18]([NH2:30])[CH3:19])[CH:15]=[C:14]([CH3:21])[N:13]=1

Komponenten

9

Edukt 4

HCID 313Hydrochloric AcidHCID 517165Ammonium AcetateHCID 5003444Sodium cyanoborohydrideHCID 18323676N-(2-bromo-4-(1-methylethyl)phenyl)-N-ethyl-4-acetyl-6-methylpyrimidinamine

Produkt 2

HCID 14923Ammonium HydroxideHCID 18323742N-(2-bromo-4-(1-methylethyl)phenyl)-N-ethyl-4-(1-aminoethyl)-6-methylpyrimidinamineAusbeute 71,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 887MethanolLösungsmittel2×HCID 6212ChloroformLösungsmittelHCID 8857Ethyl AcetateLösungsmittel2×

Versuchsvorschrift

A mixture of N-(2-bromo-4-(1-methylethyl)phenyl)-N-ethyl-4-acetyl-6-methyl-pyrimidinamine (0.5 g, 1.33 mmol), ammonium acetate (1.1 g, 14 mmol), sodium cyanoborohydride (59 mg, 0.9 mmol) and methanol (5 mL) was stirred at ambient temperature for 90 h. A concentrated HCl solution was added until the solution became acidic (pH=2), then the reaction mixture was concentrated in vacuo. The residue was taken up in water, basified with a concentrated NaOH solution and extracted three times with ether. The combined organic layers were dried over MgSO4, filtered and concentrated in vacuo to give an oil. Column chromatography (ethyl acetate:hexanes::1:1), then chloroform:methanol:NH4OH::95:0.5) gave (1) N-(2-bromo-4-(1-methylethyl)phenyl)-N-ethyl-4-(1-aminothyl)-6-methyl-pyrimidinamine (80 mg, 16% yield, Rf 0.34 (ethyl acetate:hexanes::1:1) and (2) the title product as a brown oil (180 mg, 36% yield, Rf 0.34 (chloroform:methanol:NH4OH:: 95:5:0.5)): NMR (CDCl3, 300 MHz): 7.5 (d, 1H, J=1), 7.2-7.1 (m, 2H), 6.4 (s, 1H), 4.25-4.05 (m, 1H), 3.9-3.65 (m, 2H), 3.0-2.85 (m, 1H), 2.4-2.2 (br m, 3H), 1.9-1.6 (br m, 3H), 1.3 (d, 6H, J=8), 1.2 (t, 3H, J=8); CI-HRMS (C18H25BrN4): 377.1341 (M+H), Found: 377.1330.

Aufarbeitung

  1. concentrationthe reaction mixture was concentrated in vacuo
  2. extractionextracted three times with ether
  3. dry with materialThe combined organic layers were dried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customto give an oil

Quellen und Nachweise

ORD-Eintrag
ord-4614bb76238448d8a8c90995221c0fc1
Quelldatensatz
uspto-grants-2000_08
Patentnummer
US06107301

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