Ethyl Acetate → 2-Amino-6-chloro-5-(5-chloro-2-methoxyphenyl)benzonitrile

HRID 1734585Notes

Reaction equation

HRID 1734585 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:11][CH3:12])=[C:6](B(O)O)[CH:7]=1.[NH2:13][C:14]1[CH:21]=[CH:20][C:19](Br)=[C:18]([Cl:23])[C:15]=1[C:16]#[N:17].C(=O)([O-])[O-].[Na+].[Na+].C(OCC)(=O)C>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:13][C:14]1[CH:21]=[CH:20][C:19]([C:6]2[CH:7]=[C:2]([Cl:1])[CH:3]=[CH:4][C:5]=2[O:11][CH3:12])=[C:18]([Cl:23])[C:15]=1[C:16]#[N:17]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 10340Sodium CarbonateHCID 27357515-Chloro-2-methoxyphenylboronic acidHCID 543850846-Amino-3-bromo-2-chlorobenzonitrile

Product 1

HCID 545231172-Amino-6-chloro-5-(5-chloro-2-methoxyphenyl)benzonitrileYield 92.6%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Procedure

A stirred mixture of 5.7 grams (0.020 mole) of 5-chloro-2-methoxyphenylboronic acid, 3.3 grams (0.014 mole) of 2-amino-5-bromo-6-chlorobenzonitrile (prepared in Step A of this Example), 21 mL of aqueous 2M sodium carbonate, and 0.15 gram (catalyst) of tetrakis(triphenylphosphine)palladium(0) in 50 mL of toluene was heated at reflux for about 17 hours. After this time, 50 mL of ethyl acetate was added to the reaction mixture. The organic layer was separated and washed with 50 mL of water and then with 50 mL of an aqueous solution saturated with sodium chloride. The organic layer was then dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to column chromatography on silica gel. Elution was accomplished using methylene chloride. The product-containing fractions were combined and concentrated under reduced pressure, yielding 3.8 grams of 2-amino-6-chloro-5-(5-chloro-2-methoxyphenyl)benzonitrile. The NMR spectrum was consistent with the proposed structure.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for about 17 hours
  3. customThe organic layer was separated
  4. washwashed with 50 mL of water
  5. dry with materialThe organic layer was then dried with magnesium sulfate
  6. filtrationfiltered
  7. concentrationThe filtrate was concentrated under reduced pressure to a residue
  8. washElution
  9. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-4fa995826472419f93acc656566a5d70
Source dataset
uspto-grants-1996_07
Patent number
US05534518

Reaction notes

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