3,5-Dinitrobenzoyl chloride → ethyl (S)-3-(3,5-dinitrobenzamido)-3-phenylpropionate

HRID 240228Notes

Reaction equation

HRID 240228 reaction equation
Cl.[NH2:2][C@H:3]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].C(N(CC)CC)C.[N+:23]([C:26]1[CH:27]=[C:28]([CH:32]=[C:33]([N+:35]([O-:37])=[O:36])[CH:34]=1)[C:29](Cl)=[O:30])([O-:25])=[O:24]>O1CCCC1>[N+:23]([C:26]1[CH:27]=[C:28]([CH:32]=[C:33]([N+:35]([O-:37])=[O:36])[CH:34]=1)[C:29]([NH:2][C@H:3]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1)[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6])=[O:30])([O-:25])=[O:24]

Participants

5

Reactant 3

HCID 74323,5-Dinitrobenzoyl chlorideHCID 8471TriethylamineHCID 22831526(S)-Ethyl 3-amino-3-phenylpropanoate hydrochloride

Product 1

HCID 44255974ethyl (S)-3-(3,5-dinitrobenzamido)-3-phenylpropionate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
5 °C

Procedure

11.49 g of ethyl (S)-3-amino-3-phenylpropionate hydrochloride were suspended in 100 ml of tetrahydrofuran and cooled to 0-10° C. in an icebath. After adding 14 ml of triethylamine, a solution of 11.52 g of 3,5-dinitrobenzoyl chloride in 40 ml of tetrahydrofuran was added with stirring and cooling over a period of 30 min. The cooling bath was removed, and the reaction mixture stirred for a further 120 min, in the course of which it warmed to room temperature. The reaction mixture was filtered, and the filtrate concentrated to dryness (product fraction 1). The filtercake—consisting of triethylamine hydrochloride and further product—was taken up in 100 ml of ethyl acetate and digested at 35° C. for 20 min. The suspension was filtered, and the filtercake discarded. The filtrate was concentrated to dryness under reduced pressure at 40° C. (product fraction 2). The product fractions were combined. Yield: 16.4 g; HPLC purity >97 area %. For further purification, the crude product was digested in 400 ml of water at room temperature for 2 h and then filtered. The moist yield was 15.4 g; HPLC purity 99.8 area %. The product was reacted further without further purification.

Workup

  1. temperaturecooling over a period of 30 min
  2. customThe cooling bath was removed
  3. stirringthe reaction mixture stirred for a further 120 min, in the course of which it
  4. temperaturewarmed to room temperature
  5. filtrationThe reaction mixture was filtered
  6. concentrationthe filtrate concentrated to dryness (product fraction 1)
  7. filtrationThe suspension was filtered
  8. concentrationThe filtrate was concentrated to dryness under reduced pressure at 40° C. (product fraction 2)
  9. customFor further purification
  10. waitthe crude product was digested in 400 ml of water at room temperature for 2 h
  11. filtrationfiltered
  12. customThe product was reacted further without further purification

Sources & evidence

ORD record
ord-6b7f1bfcf91546b9a67e9998fb89c797
Source dataset
uspto-grants-2014_02
Patent number
US08647882B2

Reaction notes

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