Toluene → 4-(4-(2-Amino-5-chloro-benzoyl)-phenoxymethyl) phenoxyacetic acid allyl ester

HRID 1975785Notes

Reaction equation

HRID 1975785 reaction equation
[NH2:1][C:2]1[CH:16]=[CH:15][C:14]([Cl:17])=[CH:13][C:3]=1[C:4]([C:6]1[CH:11]=[CH:10][C:9]([OH:12])=[CH:8][CH:7]=1)=[O:5].C[Si]([N-][Si](C)(C)C)(C)C.[K+].C1(C)C=CC=CC=1.Br[CH2:36][C:37]1[CH:50]=[CH:49][C:40]([O:41][CH2:42][C:43]([O:45][CH2:46][CH:47]=[CH2:48])=[O:44])=[CH:39][CH:38]=1>CN(C=O)C>[CH2:46]([O:45][C:43](=[O:44])[CH2:42][O:41][C:40]1[CH:39]=[CH:38][C:37]([CH2:36][O:12][C:9]2[CH:8]=[CH:7][C:6]([C:4](=[O:5])[C:3]3[CH:13]=[C:14]([Cl:17])[CH:15]=[CH:16][C:2]=3[NH2:1])=[CH:11][CH:10]=2)=[CH:50][CH:49]=1)[CH:47]=[CH2:48]

Participants

6

Reactant 4

HCID 1140TolueneHCID 3251421Potassium bis(trimethylsilyl)amideHCID 10891412HCID 10891412, compoundHCID 11402375Methanone, (2-amino-5-chlorophenyl)(4-hydroxyphenyl)-

Product 1

HCID 545252454-(4-(2-Amino-5-chloro-benzoyl)-phenoxymethyl) phenoxyacetic acid allyl ester

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution was formed by dissolving 2-amino-5-chloro-4'-hydroxybenzophenone (1.72 g, 8.07 mmol) in 40 mL of DMF. Potassium bis(trimethylsilyl)amide that was 0.5M in toluene (16.1 mL, 8.07 mmol, 1.0 equivalents) was added dropwise with stirring. Allyl 2-(4-bromomethylphenoxy)acetate (2.30 g, 8.07 mmol, 1.0 equivalents) was then added and the resulting orange slurry was stirred at ambient temperature for 45 minutes. The slurry was concentrated in vacuo, then diluted with CH2Cl2 (150 mL) and was extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL), then dried over sodium sulfate and concentrated in vacuo to give the product as a yellow solid which was approximately 95% pure and was taken to the next step without purification. The product had Rf of 0.55 in 50:50:2 ethyl acetate/hexane/triethylamine. The structure was confirmed by proton NMR, carbon-13 NMR, and electron impact mass spectroscopy.

Workup

  1. customA solution was formed
  2. additionwas added dropwise
  3. stirringthe resulting orange slurry was stirred at ambient temperature for 45 minutes
  4. concentrationThe slurry was concentrated in vacuo
  5. additiondiluted with CH2Cl2 (150 mL)
  6. extractionwas extracted with 1N aqueous sodium bicarbonate (100 mL) and with 1N aqueous sodium chloride (100 mL)
  7. dry with materialdried over sodium sulfate
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-6b59b1aafdf74aed89cc771490f33e88
Source dataset
uspto-grants-1994_02
Patent number
US05288514

Reaction notes

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