Ethyl Acetate → HCID 86668040、化合物

HRID 474067ノート

反応式

HRID 474067 の反応式
[Br:1][C:2]1[CH:7]=[C:6]([CH3:8])[CH:5]=[CH:4][N:3]=1.[Li+].CC([N-]C(C)C)C.[CH2:17]([O:19][C:20](Cl)=[O:21])[CH3:18].[NH4+].[Cl-].[C:25]([O:28][CH2:29][CH3:30])(=[O:27])C>C1COCC1>[CH2:17]([O:19][C:20](=[O:21])[CH:8]([C:6]1[CH:5]=[CH:4][N:3]=[C:2]([Br:1])[CH:7]=1)[C:25]([O:28][CH2:29][CH3:30])=[O:27])[CH3:18]

参加物

7

反応物 5

HCID 8857Ethyl AcetateHCID 10928Ethyl chloroformateHCID 25517Ammonium ChlorideHCID 2724682Lithium diisopropylamideHCID 27340872-Bromo-4-methylpyridine

生成物 1

HCID 86668040HCID 86668040、化合物

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

実験手順

2-Bromo-4-methylpyridine (70.0 g, 407 mmol) was added drop wise to a cooled (−78° C.) solution of LDA (2.0 M in toluene/THF/ethyl benzene, 610.4 ml, 1.22 mol) in dry THF (600 ml) for 30 min. ethylchloroformate (132.3 g, 1.22 mol) was added to the resultant reaction mixture with addition funnel at −78° C. and stirring continued for 90 min. Reaction mixture was treated with saturated NH4Cl solution and worked up with ethyl acetate by washing with water, brine followed by drying over anhy. Na2SO4. Organic layer ws concentrated under reduced pressure to obtain crude product which was purified by column chromatography with 10% ethyl acetate in Hexane to furnish title compound as a brown color oily liquid. Yield: 115.0 g (89%). TLC (10% ethyl acetate in hexane) Rf=0.15; LCMS: RtH8=1.475 [M+1]+=315.8 and 317.8; HPLC RtH9=7.30 min (86.7%); 1H NMR (400 MHz, CDCl3) δ 8.38 (d, 1H), 7.56 (t, 1H), 7.34 (dd, 1H), 4.55 (s, 1H), 4.29-4.18 (m, 4H), 1.28 (t, 6H).

後処理

  1. additionwas added to the resultant
  2. customreaction mixture
  3. additionwith addition funnel at −78° C.
  4. customReaction mixture
  5. washby washing with water, brine
  6. customby drying over anhy
  7. concentrationOrganic layer ws concentrated under reduced pressure
  8. customto obtain crude product which
  9. customwas purified by column chromatography with 10% ethyl acetate in Hexane

出典と根拠

ORDレコード
ord-c3971a32f89e4cad817d6a4627535e99
出典データセット
uspto-grants-2014_01
特許番号
US08637508B2

反応ノート

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