Nitrogen → 2-Pyridinecarboxylic acid, 3-chloro-5-cyano-, 1,1-dimethylethyl ester

HRID 627685ノート

反応式

HRID 627685 の反応式
Br[C:2]1[CH:3]=[C:4]([Cl:15])[C:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])=[N:6][CH:7]=1.[C:16]([Zn]C#N)#[N:17].N#N.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>CN(C=O)C.[Zn].C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Cl:15][C:4]1[C:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])=[N:6][CH:7]=[C:2]([C:16]#[N:17])[CH:3]=1

参加物

8

反応物 4

HCID 947NitrogenHCID 83681Tris(1,1-dimethylethyl)phosphine2 回HCID 68109709tert-Butyl 5-bromo-3-chloropyridine-2-carboxylateHCID 178514179HCID 178514179、化合物

生成物 1

HCID 867281412-Pyridinecarboxylic acid, 3-chloro-5-cyano-, 1,1-dimethylethyl ester

試薬・触媒・溶媒 3

HCID 23994Zinc触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒2 回HCID 6228Dimethylformamide溶媒

反応条件

温度
95 °C

実験手順

A mixture of tert-butyl 5-bromo-3-chloropicolinate (12 g, 41.0 mmol), dicyanozinc (3.37 g, 28.7 mmol), and zinc (0.375 g, 5.74 mmol) were suspended in DMF (82 ml) in round bottom flak. The suspension was purged with N2 and finally Pd2(dba)3 (1.878 g, 2.051 mmol), tri-tert-butylphosphine (6.2 ml, 6.15 mmol) and neat tri-tert-butylphosphine (300 mg), was added under the Ar. The r×n mixture was heated to 95° C. for 3 h. Then another 2.8 g of Pd2(dba)3 and 1.2 g of neat P ligand were added. 3.5 h later, it was cooled to RT and black precipitate was filtered out by filtration. The filtrate was diluted with 150 ml of MTBE. The organic layer was washed with 100 ml of water and brine. It was dried on MgSO4 and concentrated which was carried over to next step directly. MS m/z=261.0/263.0 (M+Na).

後処理

  1. additionwas added under the Ar
  2. temperature3.5 h later, it was cooled to RT
  3. filtrationblack precipitate was filtered out by filtration
  4. additionThe filtrate was diluted with 150 ml of MTBE
  5. washThe organic layer was washed with 100 ml of water and brine
  6. customIt was dried on MgSO4
  7. concentrationconcentrated which

出典と根拠

ORDレコード
ord-284939929b5746f68d90bb24f8fc1ce9
出典データセット
uspto-grants-2016_04
特許番号
US09309263B2

反応ノート

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