2-Bromoanisole → HCID 15871310, compound

HRID 727385Notes

Reaction equation

HRID 727385 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][C:4]=1[Mg]Br.BrC1C=CC=CC=1[O:18]C.[Mg].[NH2:21][C:22]1[N:26]([C:27]2[C:32]([Cl:33])=[CH:31][C:30]([Cl:34])=[CH:29][C:28]=2[Cl:35])[N:25]=[C:24]([S:36][CH3:37])[C:23]=1[C:38]#N.[Cl-].[NH4+]>CCOCC>[NH2:21][C:22]1[N:26]([C:27]2[C:32]([Cl:33])=[CH:31][C:30]([Cl:34])=[CH:29][C:28]=2[Cl:35])[N:25]=[C:24]([S:36][CH3:37])[C:23]=1[C:38](=[O:18])[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][C:3]=1[O:2][CH3:1]

Participants

7

Reactant 5

HCID 113582-BromoanisoleHCID 25517Ammonium ChlorideHCID 5462224MagnesiumHCID 15871316HCID 15871316, compoundHCID 178489560HCID 178489560, compound

Product 1

HCID 15871310HCID 15871310, compoundYield 14%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a solution of 2-methoxyphenylmagnesium bromide prepared from 18.7 g (0.10 mol) of 2-bromoanisole and 2.43 g (0.10 mol) of magnesium turnings in ether under dry nitrogen was added 1.6 g (5.0 mmol) of 5-amino-4-cyano-3-methylthio-1-(2,4,6-trichlorophenyl)pyrazole and the resulting mixture was stirred and refluxed for 16 hours. Upon cooling, the reaction was decomposed with 50 mL of saturated ammonium chloride solution. The organic phase was extracted with aqueous hydrogen chloride and the acidic extract was treated with 10 mL of concentrated hydrogen chloride and heated at 80°-90° C. for 10 minutes after which the mixture was cooled and made alkaline. Extraction with methylene dichloride and chromatography of the extracts with mixtures of hexane and ethyl acetate gave 313 mg (14%) of the title compound, m.p. 200°-202° C. Anal. Calcd. for C18H14O2 N3SCl3 : C, 48.82; H, 3.18; N, 9.49. Found: C, 48.54; H, 3.32; N, 9.09.

Workup

  1. temperaturerefluxed for 16 hours
  2. temperatureUpon cooling
  3. extractionThe organic phase was extracted with aqueous hydrogen chloride
  4. extractionthe acidic extract
  5. additionwas treated with 10 mL of concentrated hydrogen chloride
  6. temperatureheated at 80°-90° C. for 10 minutes after which the mixture
  7. temperaturewas cooled
  8. extractionExtraction with methylene dichloride and chromatography of the extracts with mixtures of hexane and ethyl acetate

Sources & evidence

ORD record
ord-46028d3e122844049b0d9ff6790d174c
Source dataset
uspto-grants-1998_01
Patent number
US05712303

Reaction notes

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