Water → 4-Hydroxy-3-nitrobenzonitrile

HRID 977097Notes

Reaction equation

HRID 977097 reaction equation
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=O)=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].Cl.[NH2:14]O.C([O-])=O.[Na+].O>C(O)=O>[OH:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:14])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11]

Participants

6

Reactant 4

HCID 962WaterHCID 181694-Hydroxy-3-nitrobenzaldehydeHCID 443297Hydroxyamine hydrochlorideHCID 2723810Sodium Formate

Product 1

HCID 767584-Hydroxy-3-nitrobenzonitrileYield 87.6%

Reagents, catalysts & solvents 1

HCID 284Formic AcidSolvent

Procedure

A mixture of 5.0 g of 4-hydroxy-3-nitrobenzaldehyde with 2.5 g of hydroxylamine hydrochloride and 3.6 g of sodium formate was heated under reflux in 35 ml of formic acid for 5 hours. After the reaction mixture was cooled, water was added thereto. The precipitated crystal was collected by filtration to give 4.3 g of 4-hydroxy-3-nitrobenzonitrile. 3.5 g of thioacetamide was added thereto and the mixture was heated at 80° C. for 1 hour in 12 ml of N,N-dimethylformamide saturated with hydrochloric acid. After the completion of the reaction, the reaction mixture was neutralized with 30 ml of water and 18 ml of 2N sodium hydroxide. The precipitated crystal was collected by filtration and recrystallized from ethanol to give 3.9 g of 4-hydroxy-3-nitrobenzthioamide. This product was dissolved in 30 ml of ethanol, 2.7 g of ethyl 2-chloroacetoacetate was added thereto, and the mixture was heated under reflux for 5 hours. The reaction mixture was cooled, and the precipitated crystal was collected by filtration and recrystallized from ethanol to give 3.4 g of ethyl 2-(4-hydroxy-3-nitrophenyl)-4-methyl-5-thiazolecarboxylate (yield: 37%).

Workup

  1. temperaturewas heated
  2. temperatureAfter the reaction mixture was cooled
  3. filtrationThe precipitated crystal was collected by filtration

Sources & evidence

ORD record
ord-66e09d3f93d246f6abcc7de0f38dce9c
Source dataset
uspto-grants-1997_03
Patent number
US05614520

Reaction notes

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