Phenylboronic Acid → Benzophenone (6-chloropyrimidin-4-yl)hydrazone

HRID 37885

Reaction equation

HRID 37885 reaction equation
Cl[C:2]1[CH:7]=[C:6]([Cl:8])[N:5]=[CH:4][N:3]=1.[C:9](=[N:22][NH2:23])([C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1.CC(C)([O-])C.[Na+].C1(B(O)O)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[Cl:8][C:6]1[N:5]=[CH:4][N:3]=[C:2]([NH:23][N:22]=[C:9]([C:10]2[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=2)[C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=2)[CH:7]=1

Participants

7

Reactant 5

HCID 66827Phenylboronic AcidHCID 709434,6-DichloropyrimidineHCID 79304DiphenylmethylidenehydrazineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxide

Product 1

HCID 86672326Benzophenone (6-chloropyrimidin-4-yl)hydrazone

Reagents, catalysts & solvents 1

HCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
90 °C

Procedure

10.0 g (67.1 mmol) of 4,6-dichloropyrimidine, 14.5 g (73.8 mmol) of benzophenone hydrazone, 9.03 g (94.0 mmol) of sodium tert-butoxide, 409 mg (3.36 mmol) of phenylboronic acid, 301 mg (1.34 mmol) of palladium(II) acetate and 384 mg (1.34 mmol) of rac-2,2′-bis-(diphenylphosphino)-1,1′-binaphthalene are combined. The mixture is degassed and vented twice with argon, 400 ml of dry degassed toluene are added, the mixture is again degassed and vented twice with argon and heated at 90° C. overnight. After cooling, the reaction mixture is poured into water, the aqueous phase is extracted with ethyl acetate, the combined organic phases are concentrated and the residue is taken up in a mixture of dichloromethane and diethyl ether. The precipitate that remains is filtered off with suction (and discarded), the filtrate is concentrated and the residue is purified by column chromatography on silica gel 60 (mobile phase: toluene/ethyl acetate 8:2).

Workup

  1. customThe mixture is degassed
  2. customof dry
  3. customdegassed toluene
  4. additionare added
  5. customthe mixture is again degassed
  6. temperatureAfter cooling
  7. additionthe reaction mixture is poured into water
  8. extractionthe aqueous phase is extracted with ethyl acetate
  9. concentrationthe combined organic phases are concentrated
  10. additionthe residue is taken up in a mixture of dichloromethane and diethyl ether
  11. filtrationThe precipitate that remains is filtered off with suction (and discarded)
  12. concentrationthe filtrate is concentrated
  13. customthe residue is purified by column chromatography on silica gel 60 (mobile phase: toluene/ethyl acetate 8:2)

Sources & evidence

ORD record
ord-85eeaee5f22249eba27910310d48eb54
Source dataset
uspto-grants-2013_09
Patent number
US08524699B2

Linked notes

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