Sodium Hydroxide → Methyl 4-chloro-3-cyanobenzoate

HRID 2414320Notes

Reaction equation

HRID 2414320 reaction equation
N([O-])=O.[Na+].N[C:6]1[CH:7]=[C:8]([CH:13]=[CH:14][C:15]=1[Cl:16])[C:9]([O:11][CH3:12])=[O:10].[OH-].[Na+].[Cu](C#N)[C:20]#[N:21]>O.Cl>[Cl:16][C:15]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[CH:7][C:6]=1[C:20]#[N:21]

Participants

7

Reactant 4

HCID 14798Sodium HydroxideHCID 593055Methyl 3-Amino-4-chlorobenzoateHCID 23668193Sodium NitriteHCID 178418260HCID 178418260, compound

Product 1

HCID 22644672Methyl 4-chloro-3-cyanobenzoateYield 36.8%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×

Procedure

A solution of sodium nitrite (1.28 g) in water (8 ml) was added over 10 min to a mixture of methyl 3-amino-4-chlorobenzoate (4.0 g) in water (40 ml) and concentrated hydrochloric acid (5 ml) at 0° C. After 30 min the mixture was neutralised with aqueous sodium hydroxide solution to pH˜7 then added portionwise to a solution of copper cyanide (prepared from sodium cyanide (2.87 g) and copper(I) chloride (2.23 g) in water (40 ml)) at 0° C. The mixture was stirred at room temperature for 2 h then partitioned between ethyl acetate and water. The organics were washed with water, dried and evaporated under reduced pressure. The residue was triturated with 20% ethyl acetate/isohexane to yield a solid (1.55 g).

Workup

  1. customthen partitioned between ethyl acetate and water
  2. washThe organics were washed with water
  3. customdried
  4. customevaporated under reduced pressure
  5. customThe residue was triturated with 20% ethyl acetate/isohexane

Sources & evidence

ORD record
ord-e40f46286fea4db2845ea1f91879dd65
Source dataset
uspto-grants-2004_11
Patent number
US06812226B2

Reaction notes

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