Toluene → HCID 59038011, compound

HRID 1057395Notes

Reaction equation

HRID 1057395 reaction equation
[NH:1]1[C:5]2C=CC=[CH:9][C:4]=2[N:3]=N1.[CH:10]([C:12]1[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][CH:13]=1)=O.[CH3:22][O:23][C:24]1[CH:25]=[C:26]([Mg]Br)[CH:27]=[CH:28][CH:29]=1.Br[C:33]1[CH:34]=C(OC)C=C[CH:38]=1.[Mg].[C:42]1(C)[CH:47]=CC=C[CH:43]=1>O1CCCC1.O>[CH2:34]([N:3]1[C@H:4]([CH3:9])[CH2:5][N:1]([C@H:10]([C:12]2[CH:21]=[CH:20][C:15]([C:16]([O:18][CH3:19])=[O:17])=[CH:14][CH:13]=2)[C:28]2[CH:27]=[CH:26][CH:25]=[C:24]([O:23][CH3:22])[CH:29]=2)[C@@H:42]([CH3:47])[CH2:43]1)[CH:33]=[CH2:38]

Participants

9

Reactant 6

HCID 1140TolueneHCID 15294Methyl 4-FormylbenzoateHCID 169713-BromoanisoleHCID 5462224MagnesiumHCID 178418385HCID 178418385, compoundHCID 178490745HCID 178490745, compound

Product 1

HCID 59038011HCID 59038011, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-17.5 °C

Procedure

A solution of the compound of Preparation 1 (11.55 g), benzotriazole (8.93 g) and methyl 4-formylbenzoate (12.32 g) in toluene (100 ml) was heated under reflux with azeotropic removal of water for 3 hours. The solution was cooled and added to a cold solution (−20° C.) of 3-methoxyphenylmagnesium bromide (prepared from 28.05 g of the 3-bromoanisole and 3.65 g of magnesium turnings) in tetrahydrofuran (100 ml) at such a rate as to maintain the internal temperature in the range −20 to −15° C. The resulting solution was stirred at −20° C. for 5 minutes and then warmed to room temperature, quenched with saturated aqueous ammonium chloride solution (200 ml). The layers were separated and the aqueous solution extracted with ethyl acetate (2×200 ml). The combined organic extracts were dried (MgSO4) and evaporated to dryness in vacuo. The residue was purified by column chromatography over silica gel using gradient elution (Hexane to 50% ethyl acetate/hexane) to afford the title compound, 27.95 g.

Workup

  1. temperaturewas heated
  2. temperatureThe solution was cooled
  3. temperaturewarmed to room temperature
  4. customquenched with saturated aqueous ammonium chloride solution (200 ml)
  5. customThe layers were separated
  6. extractionthe aqueous solution extracted with ethyl acetate (2×200 ml)
  7. dry with materialThe combined organic extracts were dried (MgSO4)
  8. customevaporated to dryness in vacuo
  9. customThe residue was purified by column chromatography over silica gel using gradient elution (Hexane to 50% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-9d01049262be4483925d3444201d8e40
Source dataset
uspto-grants-2003_02
Patent number
US06514975B1

Reaction notes

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