4-Amino-4'-cyanobiphenyl → HCID 68644435, compound

HRID 1158938Notes

Reaction equation

HRID 1158938 reaction equation
[CH:1]([C:3]1[C:4]([CH3:20])=[C:5]([O:10][CH2:11][C:12]2[CH:19]=[CH:18][C:15]([C:16]#[N:17])=[CH:14][CH:13]=2)[C:6]([CH3:9])=[N:7][CH:8]=1)=O.[NH2:21][C:22]1[CH:27]=[CH:26][C:25]([C:28]2[CH:33]=[CH:32][C:31]([C:34]#[N:35])=[CH:30][CH:29]=2)=[CH:24][CH:23]=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.[BH4-].[Na+]>C1C=CC=CC=1>[C:16]([C:15]1[CH:18]=[CH:19][C:12]([CH2:11][O:10][C:5]2[C:4]([CH3:20])=[C:3]([CH2:1][NH:21][C:22]3[CH:23]=[CH:24][C:25]([C:28]4[CH:33]=[CH:32][C:31]([C:34]#[N:35])=[CH:30][CH:29]=4)=[CH:26][CH:27]=3)[CH:8]=[N:7][C:6]=2[CH3:9])=[CH:13][CH:14]=1)#[N:17]

Participants

6

Reactant 4

HCID 971934-Amino-4'-cyanobiphenylHCID 521998p-Toluenesulfonic acid monohydrateHCID 4311764Sodium borohydrideHCID 86240729HCID 86240729, compound

Product 1

HCID 68644435HCID 68644435, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

A mixture of 4-(5-formyl-2,4-dimethyl-pyridin-3-yloxymethyl)-benzonitrile (23) (0.40 g, 1.5 mmol), 4-amino-4′-cyanobiphenyl (0.35 g, 1.8 mmol) and p-toluenesulfonic acid monohydrate (0.08 g, 0.45 mmol) was heated at 100° C. in benzene (15 mL) under nitrogen atmosphere with a Dean-Stark condenser for 18 hours. The solvent mixture was then evaporated and the crude product dissolved in methyl alcohol (20 mL), and to the solution was added sodium borohydride (0.56 g, 15 mmol). The reaction mixture was stirred at room temperature for 2 hours, quenched with saturated aqueous sodium bicarbonate, extracted with ethyl acetate and then back washed with water. The combined organic layer was dried over anhydrous magnesium sulfate, filtered and evaporated to dryness. The crude product was purified by column chromatography on silica gel using a gradient mixture of ethyl acetate:hexane (0:1 to 1:1) as eluant to give 4′-{[5-(4-cyano-benzyloxy)-4,6-dimethyl-pyridin-3-ylmethyl]-amino}-biphenyl-4-carbonitrile (24) (266 mg, 40% overall yield for two steps).

Workup

  1. customThe solvent mixture was then evaporated
  2. dissolutionthe crude product dissolved in methyl alcohol (20 mL)
  3. customquenched with saturated aqueous sodium bicarbonate
  4. extractionextracted with ethyl acetate
  5. washback washed with water
  6. dry with materialThe combined organic layer was dried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. customevaporated to dryness
  9. customThe crude product was purified by column chromatography on silica gel using
  10. additiona gradient mixture of ethyl acetate:hexane (0:1 to 1:1) as eluant

Sources & evidence

ORD record
ord-83fdf5c3c3584494bed2f5baed4faf30
Source dataset
uspto-grants-2010_10
Patent number
US07812037B2

Reaction notes

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