3-Bromopyridine → 3,4-Dimethyl-1-[(E)-3-(pyridin-3-yl)prop-2-enoyl]-5-phenylimidazolidin-2-one

HRID 1816009ノート

反応式

HRID 1816009 の反応式
Br[C:2]1[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=1.[C:8]([N:12]1[CH:16]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:15]([CH3:23])[N:14]([CH3:24])[C:13]1=[O:25])(=[O:11])[CH:9]=[CH2:10].CC1C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C.CCN(C(C)C)C(C)C>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:24][N:14]1[CH:15]([CH3:23])[CH:16]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[N:12]([C:8](=[O:11])/[CH:9]=[CH:10]/[C:2]2[CH:3]=[N:4][CH:5]=[CH:6][CH:7]=2)[C:13]1=[O:25]

参加物

7

反応物 4

HCID 122863-BromopyridineHCID 80271Tri-o-tolylphosphineHCID 81531DiisopropylethylamineHCID 228977581-Acryloyl-3,4-dimethyl-5-phenylimidazolidin-2-one

生成物 1

HCID 207756463,4-Dimethyl-1-[(E)-3-(pyridin-3-yl)prop-2-enoyl]-5-phenylimidazolidin-2-one

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
110 °C

実験手順

A solution of 3-bromopyridine (8.6 mL, 88.5 mmole), (4 R, 5 S)-1-acryloyl-3,4-dimethyl-5-phenylimidazolidin-2-one (14.4 g. 59 mmole), Pd(OAc)2 (662 mg, 2.95 mmole), P(o-tolyl)3 (1.80 g, 5.9 mmole), and (i-Pr)2NEt (22 mL, 124 mmole) in dry DMF (300 mL) was degassed (3×vacuum/N2 purge) then heated to 110° C. After 2 hr the mixture was cooled and poured into EtOAc. The resulting mixture was washed with H2O (3×), and the combined aqueous layers were back-extracted with EtOAc (2×). The combined organic layers were dried over MgSO4, filtered through a plug of silica gel, and concentrated. The residue was taken up in 1: EtOAc/hexanes and the solid was collected, washed with 1:1 EtOAc/hexanes, and dried in vacuo to afford a first crop of the title compound. The filtrate was concentrated and the crystallization process was repeated to afford a second crop. The total yield of the title compound was 17.53 g (92%): 1H NMR (400 MHz, CDCl3) δ 8.48-8.85 (m, 2H), 8.25 (d, J=15.9 Hz, 1 H), 7.89-7.97 (m, 1 H), 7.68 (d, J=15.9 Hz, 1 H), 7.15-7.38 (m, 6 H), 5.43 (d, J=8.5 Hz, 1 H), 3.90-4.02 (m, 1 H), 2.88 (s, 3H), 0.85 (d, J=6.6 Hz, 3 H); MS (ES) m/e 322 (M+H)+.

後処理

  1. custom(3×vacuum/N2 purge)
  2. temperatureAfter 2 hr the mixture was cooled
  3. additionpoured into EtOAc
  4. washThe resulting mixture was washed with H2O (3×)
  5. extractionthe combined aqueous layers were back-extracted with EtOAc (2×)
  6. dry with materialThe combined organic layers were dried over MgSO4
  7. filtrationfiltered through a plug of silica gel
  8. concentrationconcentrated
  9. customEtOAc/hexanes and the solid was collected
  10. washwashed with 1:1 EtOAc/hexanes
  11. customdried in vacuo

出典と根拠

ORDレコード
ord-dbceaa2adeee448c8bc749978df8ba04
出典データセット
uspto-grants-2005_04
特許番号
US06881736B1

反応ノート

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