Phenylboronic Acid → HCID 86659953, compound

HRID 2199583Notes

Reaction equation

HRID 2199583 reaction equation
Br[C:2]1[CH:7]=[C:6]([N:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][N:3]=1.[C:11](=[N:24][NH2:25])([C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.CC(C)([O-])C.[Na+].C1(B(O)O)C=CC=CC=1>C1(C)C=CC=CC=1.CCOC(C)=O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[C:12]1([C:11]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[N:24][NH:25][C:2]2[CH:7]=[C:6]([N:8]([CH3:10])[CH3:9])[CH:5]=[CH:4][N:3]=2)[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

8

Reactant 4

HCID 66827Phenylboronic AcidHCID 79304DiphenylmethylidenehydrazineHCID 117456782-Bromo-N,N-dimethylpyridin-4-amineHCID 23676156Sodium t-butoxide

Product 1

HCID 86659953HCID 86659953, compound

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 1140TolueneSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
80 °C

Procedure

To a mixture of 3.3 g (16.41 mmol) of 2-bromo-N,N-dimethylpyridin-4-amine in 40 mL of anhydrous toluene, 3.5 g (18.05 mmol) of benzophenone hydrazone, 2.2 g (23 mmol) of anhydrous sodium tert-butoxide and 100 mg (0.82 mmol) of benzeneboronic acid in 40 mL of toluene are added, under argon, at room temperature, after having degassed the reaction medium under argon, 74 mg (0.33 mmol) of palladium acetate and 205 mg (0.33 mmol) of racBINAP. The reaction medium is then heated for 4 hours at 80° C. The reaction medium is taken up in 200 mL of EtOAc, washed successively with water (3×30 mL), with saturated NaHCO3 solution (30 mL) and with brine (30 mL) and then dried over Na2SO4, filtered and concentrated under reduced pressure. The residue obtained is purified by chromatography on a column of silica gel, eluting with a DCM/MeOH gradient of from 0 to 10% MeOH. After concentrating under reduced pressure, 4.5 g of 2-[2-(diphenylmethylidene)hydrazino]-N,N-dimethylpyridin-4-amine are obtained in the form of a red solid.

Workup

  1. additionare added, under argon, at room temperature
  2. customafter having degassed the reaction medium under argon
  3. washwashed successively with water (3×30 mL), with saturated NaHCO3 solution (30 mL) and with brine (30 mL)
  4. dry with materialdried over Na2SO4
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue obtained
  8. customis purified by chromatography on a column of silica gel
  9. washeluting with a DCM/MeOH gradient of from 0 to 10% MeOH
  10. concentrationAfter concentrating under reduced pressure, 4.5 g of 2-[2-(diphenylmethylidene)hydrazino]-N,N-dimethylpyridin-4-amine
  11. customare obtained in the form of a red solid

Sources & evidence

ORD record
ord-1aaf140d213c4e0ca57d85c9b6266b07
Source dataset
uspto-grants-2016_06
Patent number
US09359329B2

Reaction notes

Loading…