Dichloromethane → 3-(4-Aminophenyl)-5-chloroisonicotinonitrile

HRID 1159448Notes

Reaction equation

Cl[C:2]1[CH:9]=[N:8][CH:7]=[C:6]([Cl:10])[C:3]=1[C:4]#[N:5].CC1(C)C(C)(C)OB([C:19]2[CH:24]=[CH:23][C:22]([NH2:25])=[CH:21][CH:20]=2)O1.C(Cl)Cl.C([O-])([O-])=O.[Na+].[Na+]>CN(C=O)C.O>[NH2:25][C:22]1[CH:23]=[CH:24][C:19]([C:2]2[CH:9]=[N:8][CH:7]=[C:6]([Cl:10])[C:3]=2[C:4]#[N:5])=[CH:20][CH:21]=1

Participants

Conditions

Temperature: 85 °C

Procedure

The product from Example 1B (3 g, 17.3 mmol), 4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenylamine (4.18 g, 19 mmol), PdCl2dppf.CH2Cl2 (300 mg), and Na2CO3 (4.5 g) were combined in DMF (25 mL) and water (10 mL). The mixture was degassed with nitrogen and heated to 85° C. overnight The mixture was allowed to cool to room temperature and partitioned between water and ethyl acetate. The organic layer was dried (Na2SO4), filtered, and the filtrate was concentrated under reduced pressure. The residue was purified via silica gel chromatography eluting with hexanes:ethyl acetate (1:1) to provide 1.4 g of the title compound. 1H NMR (300 MHz, DMSO-D6) δ ppm 5.67 (s, 2H) 6.70 (d, J=8.48 Hz, 2H) 7.40 (d, J=8.82 Hz, 2H) 8.76 (s, 1H) 8.79 (s, 1H).

Workup

customThe mixture was degassed with nitrogen
temperatureto cool to room temperature
custompartitioned between water and ethyl acetate
dry with materialThe organic layer was dried (Na2SO4)
filtrationfiltered
concentrationthe filtrate was concentrated under reduced pressure
customThe residue was purified via silica gel chromatography
washeluting with hexanes:ethyl acetate (1:1)

Sources & evidence

ORD record: ord-80bc70c4e17a40dba913b4aa23bd769a
Source dataset: uspto-grants-2010_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07812166B2

Reaction notes

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