Hydrochloric Acid → Benzoic Acid

HRID 505029Notes

Reaction equation

HRID 505029 reaction equation
N([O-])=O.[Na+].Cl.[C-]#N.[Na+].C([Cu])#N.[OH-].[Na+].N(OS(=O)(=O)O)=O.CI.[C:23]([O-:26])([O-])=[O:24].[K+].[K+].C1C(=O)N(Br)C(=O)C1.Br[C:38]1[CH:44]=[CH:43][C:41](N)=[CH:40][CH:39]=1.[Cu](C#N)C#N>>[C:23]([OH:26])(=[O:24])[C:38]1[CH:44]=[CH:43][CH:41]=[CH:40][CH:39]=1

Participants

12

Reactant 11

HCID 313Hydrochloric Acid2×HCID 6328Methyl iodideHCID 78074-BromoanilineHCID 8929Sodium Cyanide2×HCID 11430Potassium CarbonateHCID 14798Sodium HydroxideHCID 67184N-bromobutanimideHCID 82157Nitrosylsulfuric acid2×HCID 23668193Sodium NitriteHCID 178418260HCID 178418260, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 243Benzoic Acid

Procedure

Scheme 1 illustrates a representative synthesis of a 6-substituted 4-bromo-2-bromomethyl-benzoic acid methyl ester from commercially available precursors wherein the respective reaction steps comprise as follows: (a) NaNO2, aq. HCl; (b) NaCN, CuCN and HCl; (c) NaOH; (d) nitrososulphuric acid; (e) MeI and K2CO3, and (f) NBS and (PhCO2)2. Briefly, a 4-bromo-aniline may be diazotized under Sandmeyer reaction conditions, followed by conversion to the nitrile using sodium cyanide and copper cyanide. The nitrile may then be hydrolyzed to an amide by basic hydrolysis. The amide can then be hydrolyzed with nitrososulphuric acid to provide a benzoic acid, which may be converted to a methyl ester under standard conditions. The benzylic methyl group may be monobrominated with N-bromosuccinimide using benzoyl peroxide as a radical initiator to yield a desired 6-substituted 4-bromo-2-bromomethyl-benzoic acid methyl ester.

Workup

  1. customthe respective reaction steps

Sources & evidence

ORD record
ord-f7da7d0a7014454e9d9a4c7c19481bde
Source dataset
uspto-grants-2010_08
Patent number
US07781434B2

Reaction notes

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