Phenylboronic Acid → 2-[2-(Diphenylmethylidene)hydrazino]-4-methoxypyridine

HRID 889294Notes

Reaction equation

HRID 889294 reaction equation
Cl[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[CH:5]=[CH:4][N:3]=1.[C:10](=[N:23][NH2:24])([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.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>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH3:9][O:8][C:6]1[CH:5]=[CH:4][N:3]=[C:2]([NH:24][N:23]=[C:10]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:7]=1

Participants

8

Reactant 4

HCID 66827Phenylboronic AcidHCID 79304DiphenylmethylidenehydrazineHCID 634876Binap, (A+-)-HCID 19911282-Chloro-4-methoxypyridine

Product 1

HCID 591869682-[2-(Diphenylmethylidene)hydrazino]-4-methoxypyridine

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

500 mg (3.48 mmol) 2-chloro-4-methoxypyridine, 752 mg (3.83 mmol) benzophenone hydrazone, 469 mg (4.88 mmol) sodium tert-butylate, 15.6 mg (0.07 mmol) palladium(II) acetate, 21.2 mg (0.17 mmol) phenylboronic acid and 43.4 mg (0.07 mmol) racemic 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl are heated in degassed toluene at 90° C. overnight under argon. After cooling, the reaction mixture is poured into water, the aqueous phase is extracted several times with ethyl acetate and the combined organic phases are dried over sodium sulfate, filtered and concentrated. The residue is purified by means of preparative HPLC (RP18 column; mobile phase: acetonitrile/water gradient).

Workup

  1. temperatureAfter cooling
  2. extractionthe aqueous phase is extracted several times with ethyl acetate
  3. dry with materialthe combined organic phases are dried over sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe residue is purified by means of preparative HPLC (RP18 column; mobile phase: acetonitrile/water gradient)

Sources & evidence

ORD record
ord-62e4ad4e373440fb9035db514d789545
Source dataset
uspto-grants-2012_08
Patent number
US08252817B2

Reaction notes

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