Sodium Carbonate → Di-tert-butyl(2-chloro-6-phenylpyridin-3-yl)imidodicarbonate

HRID 1256668ノート

反応式

HRID 1256668 の反応式
[C:1]([O:5][C:6]([N:8]([C:16]1[C:17]([Cl:23])=[N:18][C:19](Cl)=[CH:20][CH:21]=1)[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])=[O:7])([CH3:4])([CH3:3])[CH3:2].[C:24]1(B(O)O)[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C(=O)([O-])[O-].[Na+].[Na+].O1CCOCC1>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.O.CN(C=O)C>[C:1]([O:5][C:6]([N:8]([C:16]1[C:17]([Cl:23])=[N:18][C:19]([C:24]2[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=2)=[CH:20][CH:21]=1)[C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])=[O:7])([CH3:4])([CH3:3])[CH3:2]

参加物

8

反応物 4

HCID 10340Sodium CarbonateHCID 312751,4-DioxaneHCID 66827Phenylboronic AcidHCID 58387587Di-tert-butyl(2,6-dichloropyridin-3-yl)imidodicarbonate

生成物 1

HCID 57745583Di-tert-butyl(2-chloro-6-phenylpyridin-3-yl)imidodicarbonate収率 39.2%

試薬・触媒・溶媒 3

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 6228Dimethylformamide溶媒

反応条件

温度
85 °C

実験手順

2,6-dichloropyridin-3-amine (9.39 g, 57.6 mmol), di-tert-butyldicarbonate (503 g, 230 mmol), DMAP (0.704 g, 5.76 mmol) and triethylamine (16.06 mL, 115 mmol) were combined in DCM (230 mL) and stirred at RT overnight. The solvent was evaporated and the residue was triturated with acetonitrile and filtered to provide di-tert-butyl(2,6-dichloropyridin-3-yl)imidodicarbonate. Di-tert-butyl(2,6-dichloropyridin-3-yl)imidodicarbonate (27.7 g, 76 mmol), phenyl boronic acid (13.95, 114 mmol) and sodium carbonate (114 mL, 229 mmol, 2M) were combined with dioxane (692 ml) and DMF (46 ml). The solution was purged with N2 for 20 min. Tetrakis(triphenylphosphine)palladium(0) (4.41 g, 3.81 mmol) was added and reaction heated to 85° C. for 3 h, then cooled to RT and stirred overnight. Reaction was poured into H2O (100 ml) and extracted with EtOAc (2×100) ml. The combined organics were washed with brine and dried over Na2SO4. Crude product was purified by flash chromatography on ISCO 330 g column. (0-20% EtOAc/Heptane). Major spot (TLC 10:1 Heptane/EtOAc) isolated to give 12.06 g of di-tert-butyl(2-chloro-6-phenylpyridin-3-yl)imidodicarbonate as a white solid. 1H NMR (CDCl3) δ 8.01 (d, J=7.0 Hz, 2H), 7.69 (d, J=8.1 Hz, 1H), 7.58 (d, J=8.1 Hz, 1H), 7.41-7.48 (m, 3H), 1.40 (s, 18H); MS: cal'd 405 (MH+), exp 405 (MH+).

後処理

  1. customThe solution was purged with N2 for 20 min
  2. customreaction
  3. temperaturecooled to RT
  4. customReaction
  5. extractionextracted with EtOAc (2×100) ml
  6. washThe combined organics were washed with brine
  7. dry with materialdried over Na2SO4
  8. customCrude product was purified by flash chromatography on ISCO 330 g column
  9. customMajor spot (TLC 10:1 Heptane/EtOAc) isolated

出典と根拠

ORDレコード
ord-d0c99516f23747068e43179de15bc784
出典データセット
uspto-grants-2013_06
特許番号
US08461189B2

反応ノート

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