Nitrogen → tert-Butyl 3-(3-methylpyridin-2-yl)benzoate

HRID 402554

反応式

HRID 402554 の反応式
Br[C:2]1[C:7]([CH3:8])=[CH:6][CH:5]=[CH:4][N:3]=1.C([O-])([O-])=O.[K+].[K+].N#N.[C:17]([O:21][C:22]([C:24]1[CH:25]=[C:26](B(O)O)[CH:27]=[CH:28][CH:29]=1)=[O:23])([CH3:20])([CH3:19])[CH3:18].C(Cl)Cl.CS(O)(=O)=O.[OH-].[Na+]>C1(C)C=CC=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].O>[C:17]([O:21][C:22](=[O:23])[C:24]1[CH:25]=[CH:26][CH:27]=[C:28]([C:2]2[C:7]([CH3:8])=[CH:6][CH:5]=[CH:4][N:3]=2)[CH:29]=1)([CH3:20])([CH3:18])[CH3:19]

参加物

11

反応物 7

HCID 947NitrogenHCID 6344DichloromethaneHCID 6395Methanesulfonic AcidHCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 2208322-Bromo-3-methylpyridineHCID 2773299(3-((Tert-butoxy)carbonyl)phenyl)boronic acid

生成物 1

HCID 57516851tert-Butyl 3-(3-methylpyridin-2-yl)benzoate収率 82%

試薬・触媒・溶媒 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 962Water溶媒2 回HCID 1140Toluene溶媒

反応条件

温度
80 °C

実験手順

2-Bromo-3-methylpyridine (1.0 eq) was dissolved in toluene (12 vol). K2CO3 (4.8 eq) was added, followed by water (3.5 vol). The resulting mixture was heated to 65° C. under a stream of N2 for 1 hour. 3-(t-Butoxycarbonyl)phenylboronic acid (1.05 eq) and Pd(dppf)Cl2.CH2Cl2 (0.015 eq) were then added, and the mixture was heated to 80° C. After 2 hours, the heat was turned off, water was added (3.5 vol), and the layers were allowed to separate. The organic phase was then washed with water (3.5 vol) and extracted with 10% aqueous methanesulfonic acid (2 eq MsOH, 7.7 vol). The aqueous phase was made basic with 50% aqueous NaOH (2 eq) and extracted with EtOAc (8 vol). The organic layer was concentrated to afford crude tert-butyl-3-(3-methylpyridin-2-yl)benzoate (82%) that was used directly in the next step.

後処理

  1. customto separate
  2. washThe organic phase was then washed with water (3.5 vol)
  3. extractionextracted with EtOAc (8 vol)
  4. concentrationThe organic layer was concentrated

出典と根拠

ORDレコード
ord-3c7c2f5ff82146528e888c36b85ef494
出典データセット
uspto-grants-2014_06
特許番号
US08742122B2

関連ノート

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