Nitric Acid → ST50929432

HRID 745881Notes

Reaction equation

HRID 745881 reaction equation
[CH3:1][O:2][C:3](=[O:12])[NH:4][C:5]1[CH:10]=[CH:9][C:8]([CH3:11])=[CH:7][CH:6]=1.[N+:13]([O-])([OH:15])=[O:14].O.[OH-].[Na+]>C(Cl)Cl>[CH3:1][O:2][C:3](=[O:12])[NH:4][C:5]1[CH:10]=[CH:9][C:8]([CH3:11])=[C:7]([N+:13]([O-:15])=[O:14])[CH:6]=1

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 962WaterHCID 14798Sodium HydroxideHCID 528092CARBAMIC ACID, (4-METHYLPHENYL)-, METHYL ESTER

Product 1

HCID 844317ST50929432

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
20 °C

Procedure

100 ml of methylene chloride are introduced into a 2 l four-necked flask equipped with a stirrer, reflux condenser, thermometer and two dropping funnels, and 165.2 g (1 mol) of 4-tolylcarbamic acid methyl ester, dissolved in 400 ml of methylene chloride, and 109.3 g of 98% strength (1.7 mols) nitric acid dissolved in 150 ml of methylene chloride are added simultaneously in the course of 1 hour, at 20° C. and under normal pressure, the temperature being maintained by external cooling. After completion of the dropwise addition, the mixture is stirred for a further hour at 20° C., the resulting solution is extracted twice with 100 ml of water at a time, and the organic solvent is then distilled off. Yield: 209.3 g of crude product, of melting point 96° to 102° C. This crude product is introduced into dilute sodium hydroxide solution, consisting of 450 ml of water and 112 g (2.8 mols) of NaOH, and the mixture is heated to 95° C. and kept at this temperature for 3 hours, whilst distilling off the methanol formed during hydrolysis of the 2-nitro-4-tolylcarbamic acid methyl ester to the amino group. The mixture is cooled to 60° C. and stirred for a further 30 minutes at 60° C., and the product is filtered off and washed alkali-free with water. The moist product is dried to constant weight in vacuo at 60° C. Yield: 144.4 g of dry product (94.6% of theory); purity: 99.7%.

Workup

  1. customequipped with a stirrer
  2. temperaturereflux condenser
  3. additionare added simultaneously in the course of 1 hour, at 20° C. and under normal pressure
  4. temperaturethe temperature being maintained by external cooling
  5. additionAfter completion of the dropwise addition
  6. extractionthe resulting solution is extracted twice with 100 ml of water at a time
  7. distillationthe organic solvent is then distilled off
  8. additionThis crude product is introduced into dilute sodium hydroxide solution
  9. temperaturethe mixture is heated to 95° C.
  10. distillationwhilst distilling off the methanol

Sources & evidence

ORD record
ord-379a2e94f75049d8bfc1c2df23eb967e
Source dataset
uspto-grants-1986_07
Patent number
US04600797

Reaction notes

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