Sodium Carbonate → 4-[4-(1-Tert-butoxycarbonylamino-1-methylethyl)phenyl]-2,5-dichloropyrimidine

HRID 1359449

反応式

HRID 1359449 の反応式
C([O-])([O-])=O.[Na+].[Na+].[Cl:7][C:8]1[N:13]=[C:12](Cl)[C:11]([Cl:15])=[CH:10][N:9]=1.CC1(C)C(C)(C)OB([C:24]2[CH:29]=[CH:28][C:27]([C:30]([NH:33][C:34](=[O:40])[O:35][C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:32])[CH3:31])=[CH:26][CH:25]=2)O1>COCCOC.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:36]([O:35][C:34]([NH:33][C:30]([C:27]1[CH:26]=[CH:25][C:24]([C:12]2[C:11]([Cl:15])=[CH:10][N:9]=[C:8]([Cl:7])[N:13]=2)=[CH:29][CH:28]=1)([CH3:32])[CH3:31])=[O:40])([CH3:37])([CH3:38])[CH3:39]

参加物

7

反応物 3

HCID 10340Sodium CarbonateHCID 2372592,4,5-TrichloropyrimidineHCID 231344434-[2-(Boc-amino)-2-propyl]phenylboronic Acid Pinacol Ester

生成物 1

HCID 181832304-[4-(1-Tert-butoxycarbonylamino-1-methylethyl)phenyl]-2,5-dichloropyrimidine収率 81.7%

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 80711,2-Dimethoxyethane溶媒

実験手順

2M aqueous Na2CO3 (4.7 ml, 9.4 mmol) was added to a solution of 2,4,5-trichloropyrimidine [Chesterfield, J.; McOmie, J. F. W.; Sayer, E. R.; J. Chem. Soc. (1955) 3478-3481] (1.18 g, 6.44 mmol), tert-butyl N-{1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]1-methylethyl}carbamate (1.55 g, 4.29 mmol) and tetrakis(triphenylphosphine)palladium (O) (150 mg, 0.13 mmol) in ethyleneglycol dimethylether (20 ml) under N2 and the mixture heated to reflux for 6 h. The reaction was diluted with H2O (30 ml) and extracted with ethyl acetate (3×50 ml), the combined ethyl acetate extracts were washed with brine (30 ml), dried (MgSO4) and concentrated in vacuo. The crude product was purified by column chromatography (SiO2, 15% ethyl acetate in hexane) to give 4-[4-(1-tert-butoxycarbonylamino-1-methylethyl)phenyl]-2,5-dichloropyrimidine as a white solid (1.34 g). δH (d6DMSO) 8.62 (1H, s), 7.90 (2H, d, J 8.6 Hz), 7.54 (2H, dt, J 8.7, 2.1 Hz), 5.02 (1H, bs), 1.65 (6H, s) and 1.37 (9H, s).

後処理

  1. temperaturethe mixture heated
  2. temperatureto reflux for 6 h
  3. extractionextracted with ethyl acetate (3×50 ml)
  4. washthe combined ethyl acetate extracts were washed with brine (30 ml)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by column chromatography (SiO2, 15% ethyl acetate in hexane)

出典と根拠

ORDレコード
ord-de03458ef4724dff92ed81cde0fe65f9
出典データセット
uspto-grants-2003_07
特許番号
US06600037B1

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