Isoamyl Nitrite → HCID 22013528, compound

HRID 1735644Notes

Reaction equation

HRID 1735644 reaction equation
N(OCCC(C)C)=O.[Cl:9][C:10]1[CH:11]=[C:12]([O:16][CH3:17])[CH:13]=[CH:14][CH:15]=1.[Cl:18][C:19]1[CH:25]=[C:24]([Cl:26])[C:23]([Cl:27])=[CH:22][C:20]=1N>>[Cl:9][C:10]1[CH:11]=[C:12]([O:16][CH3:17])[CH:13]=[CH:14][C:15]=1[C:20]1[CH:22]=[C:23]([Cl:27])[C:24]([Cl:26])=[CH:25][C:19]=1[Cl:18]

Participants

4

Reactant 3

HCID 8053Isoamyl NitriteHCID 124872,4,5-TrichloroanilineHCID 178333-Chloroanisole

Product 1

HCID 22013528HCID 22013528, compound

Procedure

Isoamyl nitrite (18.8 mL, 0.140 mol) was added portionwise over the course of 1 hour to a mixture of 3-chloroanisole (100 g, 0.70 mol) and 2,4,5-trichloroaniline (13.75 g, 0.070 mol) at 120° C. under nitrogen and the reaction was allowed to stir an additional 18 hours, and then distilled (0.2 mmHg, 160°-185° C.) to yield 14.07 g (62%). A 300 mg portion of the distillate was further purified via flash chromatography (silica gel, hexane eluent). Fraction 1 (32.2 mg, Rf=0.33; GC RT=14.44 minutes) was identified as 2',4,4',5'-tetrachloro-2-methoxybiphenyl. Fraction 2 (75.2 mg, Rf=0.22) contained a mixture of two products in a 40:60 ratio. Through subsequent demethylation and separation, these were determined to be the 2,2',4',5'-tetrachloro-6-methoxy and 2,2',4',5'-tetrachloro-4-methoxybiphenyl derivatives (GC retention time=14.01, 14.69 minutes respectively).

Workup

  1. distillationdistilled (0.2 mmHg, 160°-185° C.)
  2. customto yield 14.07 g (62%)
  3. distillationA 300 mg portion of the distillate was further purified via flash chromatography (silica gel, hexane eluent)
  4. additiona mixture of two products in a 40:60 ratio
  5. customThrough subsequent demethylation and separation
  6. customGC retention time=14.01, 14.69 minutes

Sources & evidence

ORD record
ord-18b8111b9c2e458bacea0c857698adcf
Source dataset
uspto-grants-1996_07
Patent number
US05538852

Reaction notes

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