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

HRID 82339

反応式

HRID 82339 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) is dissolved in toluene (12 vol). K2CO3 (4.8 eq) is added followed by water (3.5 vol) and the mixture 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) are then added and the mixture is heated to 80° C. After 2 hours, the heat is turned off, water is added (3.5 vol) and the layers are allowed to separate. The organic phase is then washed with water (3.5 vol) and extracted with 10% aqueous methanesulfonic acid (2 eq MsOH, 7.7 vol). The aqueous phase is made basic with 50% aqueous NaOH (2 eq) and extracted with EtOAc (8 vol). The organic layer is concentrated to afford crude tert-butyl-3-(3-methylpyridin-2-yl)benzoate (82%) that is used directly in the next step.

後処理

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

出典と根拠

ORDレコード
ord-84731088f4f743a9ac8c2caf4f96cd92
出典データセット
uspto-grants-2014_09
特許番号
US08846718B2

関連ノート

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