Chlorosuccinimide → 3',6'-Dichloro-3,5-dimethyl-2,2'-bipyridine

HRID 2172880Notes

Reaction equation

HRID 2172880 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]([C:8]2[C:13]([CH3:14])=[CH:12][C:11]([CH3:15])=[CH:10][N:9]=2)[CH:5]=[CH:4][CH:3]=1.C1C(=O)N([Cl:23])C(=O)C1>CC(O)=O.CC([O-])=O.CC([O-])=O.[Pd+2]>[Cl:23][C:5]1[C:6]([C:8]2[C:13]([CH3:14])=[CH:12][C:11]([CH3:15])=[CH:10][N:9]=2)=[N:7][C:2]([Cl:1])=[CH:3][CH:4]=1

Participants

5

Reactant 2

HCID 31398ChlorosuccinimideHCID 866919076'-Chloro-3,5-dimethyl-2,2'-bipyridine

Product 1

HCID 866919083',6'-Dichloro-3,5-dimethyl-2,2'-bipyridineYield 69.2%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 6′-chloro-3,5-dimethyl-2,2′-bipyridine (300 mg, 1.37 mmol), NCS (202 mg, 1.51 mmol), and Pd(OAc)2 (31.4 mg, 0.137 mmol) in AcOH (9.15 mL) was heated to 120° C. in a sealed microwave vial using an oil bath. After 20 h, the reaction was removed from heat and concentrated. Took up the residue in EtOAc, filtered off the solid through a glass fiber filter, and washed with 1:1 EtOAc/heptane. The filtrate was concentrated and purified on Biotage 25S column, eluting with 0-25% EtOAc/heptane to get 240 mg (69%) of the title compound as an off-white solid. m/z (APCI+) for C12H10N2Cl2 253.00 (M+H)+. 1H NMR (400 MHz, DMSO-d6) δ ppm 8.33 (s, 1 H) 8.16 (d, J=8.59 Hz, 1 H) 7.66 (d, J=8.59 Hz, 1 H) 7.61 (s, 1 H) 2.34 (s, 3 H) 2.08 (s, 3 H).

Workup

  1. customthe reaction was removed
  2. temperaturefrom heat
  3. concentrationconcentrated
  4. filtrationTook up the residue in EtOAc, filtered off the solid through a glass fiber
  5. filtrationfilter
  6. washwashed with 1:1 EtOAc/heptane
  7. concentrationThe filtrate was concentrated
  8. custompurified on Biotage 25S column
  9. washeluting with 0-25% EtOAc/heptane

Sources & evidence

ORD record
ord-d4e34e34d8494cd1acc0f45b14a90b36
Source dataset
uspto-grants-2015_06
Patent number
US09056865B2

Reaction notes

Loading…