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

HRID 627685노트

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HRID 627685 반응식
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

참가 물질

8

반응물 4

HCID 947NitrogenHCID 83681Tris(1,1-dimethylethyl)phosphine2회HCID 68109709tert-Butyl 5-bromo-3-chloropyridine-2-carboxylateHCID 178514179HCID 178514179, 화합물

생성물 1

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

시약·촉매·용매 3

HCID 23994Zinc촉매HCID 9811564Bis(dibenzylideneacetone)palladium촉매2회HCID 6228Dimethylformamide용매

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온도
95 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-284939929b5746f68d90bb24f8fc1ce9
출처 데이터셋
uspto-grants-2016_04
특허 번호
US09309263B2

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