Dimethylformamide → Methyl 2-chloro-5-cyanobenzoate

HRID 219855

反応式

HRID 219855 の反応式
Br[C:2]1[CH:3]=[CH:4][C:5]([Cl:12])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8].[CH3:13][N:14](C=O)C>[C-]#N.[Zn+2].[C-]#N.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].C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].[Zn].C([O-])(=O)C.[Zn+2].C([O-])(=O)C>[Cl:12][C:5]1[CH:4]=[CH:3][C:2]([C:13]#[N:14])=[CH:11][C:6]=1[C:7]([O:9][CH3:10])=[O:8]

参加物

8

反応物 2

HCID 6228DimethylformamideHCID 842098Methyl 5-bromo-2-chlorobenzoate

生成物 1

HCID 16659388Methyl 2-chloro-5-cyanobenzoate収率 98%

試薬・触媒・溶媒 5

HCID 11186Zinc cyanide (Zn(CN)2)触媒HCID 11192Zinc Acetate触媒HCID 23994Zinc触媒HCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)触媒HCID 9811564Bis(dibenzylideneacetone)palladium触媒

反応条件

温度
90 °C

実験手順

Methyl 5-bromo-2-chlorobenzoate (2 g; 8.02 mmol; 1 eq.), zinc cyanide (564.79 mg; 4.81 mmol; 0.60 eq.), tris(dibenzylideneacetone)dipalladium(0) (58.73 mg; 0.06 mmol; 0.01 eq.), 1,1′-bis(diphenylphosphino)ferrocene (71.11 mg; 0.13 mmol; 0.02 eq.), zinc (20.97 mg; 0.32 mmol; 0.04 eq.) and zinc acetate (58.83 mg; 0.32 mmol; 0.04 eq.) were put in dry DMF (20 mL). The reaction mixture was purged with N2 and then heated to 90° C. for 3 hours. The reaction mixture was cooled to RT, filtered over a pad of celite and washed with EtOAc. The organic phase was washed with water, brine, dried over MgSO4 and concentrated to afford a brown solid purified by flash chromatography eluting with cHex-EtOAc 8:2 affording the title compound as a yellow solid. It was washed with EtOH and dried under vacuum affording the title compound as a yellow solid (1.55 g, 98%). 1H NMR (DMSO-d6, 300 MHz) δ 8.29 (m, 1H), 8.09-8.06 (m, 1H), 7.83-7.81 (m, 1H), 3.89 (s, 3H). LC/MS (Method B): 197.0 (M+H)+. HPLC (Method A) Rt 3.70 min (Purity: 83.7%)

後処理

  1. customThe reaction mixture was purged with N2
  2. temperatureThe reaction mixture was cooled to RT
  3. filtrationfiltered over a pad of celite
  4. washwashed with EtOAc
  5. washThe organic phase was washed with water, brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customto afford a brown solid
  9. custompurified by flash chromatography
  10. washeluting with cHex-EtOAc 8:2 affording the title compound as a yellow solid
  11. washIt was washed with EtOH
  12. customdried under vacuum

出典と根拠

ORDレコード
ord-3b933cf001944b0c82c66db484944da5
出典データセット
uspto-grants-2012_06
特許番号
US08202865B2

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