Hydrochloric Acid → 3-Bromo-5-chlorotoluene

HRID 917539Notes

Reaction equation

HRID 917539 reaction equation
N[C:2]1[C:7]([Cl:8])=[CH:6][C:5]([Br:9])=[CH:4][C:3]=1[CH3:10].Cl.N([O-])=O.[Na+].O[PH2]=O>C(O)(=O)C.O>[Cl:8][C:7]1[CH:2]=[C:3]([CH3:10])[CH:4]=[C:5]([Br:9])[CH:6]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 27696264-Bromo-2-chloro-6-methylanilineHCID 4124402Phosphinic AcidHCID 23668193Sodium Nitrite

Product 1

HCID 107746383-Bromo-5-chlorotolueneYield 81.1%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent2×

Conditions

Temperature
0 °C

Procedure

Step G1. To an ice-water-cooled and stirred solution of 2-amino-5-bromo-3-chlorotoluene (12 g, 54 mmol) in a mixture of 100 mL of acetic acid, 43 mL of H2O and 11.5 mL of concentrated HCl was added dropwise a solution of NaNO2 (4.48 g, 65 mmol) in 15 mL of H2O. The reaction mixture was stirred for 30 min and was then added to an 112 mL solution of 50% H3PO2 cooled at 0° C. After being stirred for 6 h at 0° C., the reaction mixture was allowed to stand at room temperature overnight. The solid was filtered and washed with water, then dried in vacuum. 3-Chloro-5-bromo-toluene (9 g, 81%) was obtained as brown solid. Crystals. 1H NMR (CDCl3): δ 2.31 (s, 3H), 7.10 (s, 1H), 7.21 (s, 1H), 7.31 (s, 1H).

Workup

  1. stirringAfter being stirred for 6 h at 0° C.
  2. waitto stand at room temperature overnight
  3. filtrationThe solid was filtered
  4. washwashed with water
  5. customdried in vacuum

Sources & evidence

ORD record
ord-8b70b921f7cf4718b4ea13c1719f3c02
Source dataset
uspto-grants-2007_09
Patent number
US07273882B2

Reaction notes

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