Hydrochloric Acid → 4-Chloro-3-nitro-1,1'-biphenyl

HRID 652262Notes

Reaction equation

HRID 652262 reaction equation
[Cl:1][C:2]1[CH:8]=[CH:7][C:5](N)=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].Cl.N([O-])=O.[Na+].O.O.O.[C:20]([O-])(=O)[CH3:21].[Na+]>O.C1C=CC=CC=1>[Cl:1][C:2]1[CH:8]=[CH:7][C:5]([C:21]2[CH:20]=[CH:4][CH:3]=[CH:2][CH:8]=2)=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 124774-Chloro-3-nitroanilineHCID 23665404Sodium Acetate TrihydrateHCID 23668193Sodium Nitrite

Product 1

HCID 137921574-Chloro-3-nitro-1,1'-biphenylYield 56%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent3×

Conditions

Temperature
0 °C

Procedure

A mixture of 100 g (0.55 mole) of 97% purity 4-chloro-3-nitroaniline, 200 ml of concentrated hydrochloric acid and 130 ml of water was heated to reflux and then cooled to 0° C. To the resulting slurry was added dropwise a solution of 49 g (0.71 mole)of sodium nitrite in 70 ml of water over a 45 min period while maintaining the temperature at 0°-5° C. To this cold solution was added 1.3 liters of benzene (cooled to 5° C. and the mixture was stirred vigorously while a solution of 190 g sodium acetate trihydrate in 400 ml of water was added over a period of 1 hr. Vigorous stirring was continued first for 3 hr at 5° C. and then for 40 hr at ambient temperature. The organic layer was separated, washed with dilute sodium hydroxide and concentrated under reduced pressure. The residue was purified by chromatography on silica gel, eluting with 30% benzene in ligroin. Recrystallization of the isolated solid from cyclohexane-ligroin gave 71.3 g (56%) of the title product as pale yellow crystals, m.p. 43°-44° C.

Workup

  1. temperaturewas heated
  2. temperatureto reflux
  3. temperaturewhile maintaining the temperature at 0°-5° C
  4. temperaturecooled to 5° C.
  5. additionwas added over a period of 1 hr
  6. waitfor 40 hr at ambient temperature
  7. customThe organic layer was separated
  8. washwashed with dilute sodium hydroxide
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by chromatography on silica gel
  11. washeluting with 30% benzene in ligroin
  12. customRecrystallization of the isolated solid from cyclohexane-ligroin

Sources & evidence

ORD record
ord-fde4cce6fbff4fbab24f606f369b8f1e
Source dataset
uspto-grants-1987_06
Patent number
US04670566

Reaction notes

Loading…