Cesium carbonate → HCID 72211849, compound

HRID 2369552Notes

Reaction equation

HRID 2369552 reaction equation
Cl[C:2]1[N:9]=[CH:8][CH:7]=[C:6]([Cl:10])[C:3]=1[CH:4]=[O:5].[CH3:11]B1OB(C)OB(C)O1.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.O.C(OCC)(=O)C.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]>[Cl:10][C:6]1[C:3]([CH:4]=[O:5])=[C:2]([CH3:11])[N:9]=[CH:8][CH:7]=1

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 574072TrimethylboroxineHCID 150539852,4-Dichloropyridine-3-carbaldehyde

Product 1

HCID 72211849HCID 72211849, compoundYield 16.4%

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 2,4-dichloronicotinaldehyde (1.1 g, 6.25 mmol), 2,4,6-trimethyl-1,3,5,2,4,6-trioxatriborinane (0.942 g, 7.50 mmol), Cs2CO3 (6.11 g, 18.75 mmol) and PdCl2(dppf) (0.229 g, 0.312 mmol) in 1,4-dioxane (9 mL) and water (1 mL) was heated at 100° C. for 18 h. After cooling, the mixture was diluted with ethyl acetate (15 mL) and water (20 mL). The ethyl acetate layer was dried over Na2SO4, concentrated and purified by silica gel chromatography to afford 4-chloro-2-methylnicotinaldehyde (0.16 g, 1.028 mmol, 16% yield) as a yellow solid 1H NMR (400 MHz, CDCl3) δ 10.69 (s, 1H), 8.52 (d, J=7.2 Hz, 1H), 7.32 (d, J=7.2 Hz, 1H), 2.83 (s, 3H).

Workup

  1. temperatureAfter cooling
  2. dry with materialThe ethyl acetate layer was dried over Na2SO4
  3. concentrationconcentrated
  4. custompurified by silica gel chromatography

Sources & evidence

ORD record
ord-7784a8803ca54bf2a3d7723e9d35c22c
Source dataset
uspto-grants-2014_04
Patent number
US08703953B2

Reaction notes

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