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

HRID 1251507노트

반응식

HRID 1251507 반응식
[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>CO.C(Cl)(Cl)Cl.C(OCC)(=O)C>[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

참가 물질

9

반응물 4

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

생성물 2

HCID 14923Ammonium HydroxideHCID 18323742N-(2-bromo-4-(1-methylethyl)phenyl)-N-ethyl-4-(1-aminoethyl)-6-methylpyrimidinamine수율 71.7%

시약·촉매·용매 3

HCID 887Methanol용매2회HCID 6212Chloroform용매HCID 8857Ethyl Acetate용매

실험 절차

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: then chloroform:methanol:NH4OH::95:5:0.5) 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.

후처리

  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

출처 및 근거

ORD 기록
ord-882dd9b79714471bb16885b707bce024
출처 데이터셋
uspto-grants-2002_01
특허 번호
US06342503B1

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