Hydrochloric Acid → 1-Chloro-2,4-dimethyl-5-nitrobenzene

HRID 857449Notes

Reaction equation

HRID 857449 reaction equation
N([O-])=O.[Na+].[N+:5]([C:8]1[CH:14]=[C:12](N)[C:11]([CH3:15])=[CH:10][C:9]=1[CH3:16])([O-:7])=[O:6].[ClH:17]>O.[Cu]Cl>[Cl:17][C:12]1[CH:14]=[C:8]([N+:5]([O-:7])=[O:6])[C:9]([CH3:16])=[CH:10][C:11]=1[CH3:15]

Participants

6

Reactant 3

HCID 313Hydrochloric Acid2×HCID 2280072,4-Dimethyl-5-nitroanilineHCID 23668193Sodium Nitrite

Product 1

HCID 34565221-Chloro-2,4-dimethyl-5-nitrobenzeneYield 47%

Reagents, catalysts & solvents 2

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent2×

Procedure

A solution of sodium nitrite (7.2 g, 0.1 mol) in water (20 mL) was added dropwise over 45 min at <5° C. to a stirred suspension of 5-nitro-2,4-xylidine (16.6 g, 0.1 mol) in conc. hydrochloric acid (300 mL). After complete addition the reaction was stirred at <5° C. for 1 h then a solution of copper(I)chloride (16.0 g, 0.16 mol) in conc. hydrochloric acid (50 mL) was added dropwise over 20 min at <5° C. (CARE: effervescence at first). The reaction was then warmed from 0° C. to room temperature and stirred for 18 h. The mixture was then carefully poured into water (1 L) and extracted with ethyl acetate (3×300 mL). The combined organic extracts were dried (magnesium sulfate), filtered and the solvent removed under vacuum to leave a crude oil. The oil was purified by flash column chromatography (SiO2; heptane) to give the product as a yellow oil (8.8 g, 47%). IR νmax (film)/cm−1 3103, 2985, 2935, 2863, 2744, 2432, 1610, 1572, 1518, 1480, 1454, 1384, 1346, 1286, 1266, 1244, 1197, 1166, 1157, 1107, 1036, 982, 894, 842, 759, 746, 725, 704, 646 and 602; NMR δH (400 MHz; CDCl3) 8.01 (1H, s), 7.20 (1H, s), 2.56 (3H, s), 2.41 (3H, s).

Workup

  1. additionAfter complete addition the reaction
  2. temperatureThe reaction was then warmed from 0° C. to room temperature
  3. stirringstirred for 18 h
  4. extractionextracted with ethyl acetate (3×300 mL)
  5. dry with materialThe combined organic extracts were dried (magnesium sulfate)
  6. filtrationfiltered
  7. customthe solvent removed under vacuum
  8. customto leave a crude oil
  9. customThe oil was purified by flash column chromatography (SiO2; heptane)

Sources & evidence

ORD record
ord-8b7a1c08eb5246adba4eaf415e12b689
Source dataset
uspto-grants-2006_12
Patent number
US07145009B2

Reaction notes

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