Dimethylformamide → HCID 54464324, compound

HRID 1781312Notes

Reaction equation

HRID 1781312 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C@H:10]([CH3:23])[C:11]([NH:13][C@H:14]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH2:15][OH:16])=[O:12])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].C(Cl)(=O)C(Cl)=O.[N+](C1C=C(C(C)C(O)=O)C=CC=1)([O-])=O.CN(C)C=O>ClCCCl>[N+:1]([C:4]1[CH:5]=[C:6]([C@@H:10]([CH3:23])[C:11]([NH:13][C@H:14]([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[CH2:15][OH:16])=[O:12])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].[N+:1]([C:4]1[CH:5]=[C:6]([C@H:10]([CH3:23])[C:11]([NH:13][C@H:14]([C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[CH2:15][OH:16])=[O:12])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2]

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 11116940HCID 11116940, compoundHCID 54464324HCID 54464324, compound

Product 2

HCID 54464324HCID 54464324, compoundHCID 54464325HCID 54464325, compound

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
20 °C

Procedure

J (S)-2-(3-Nitrophenyl)-N-[(R)-2-hydroxy-1-phenylethyl]propionamide may be prepared in the following manner: 17.2 cm3 of oxalyl chloride are added slowly to a mixture containing 39.0 g of (RS)-2-(3-nitrophenyl)propionic acid and 0.5 cm3 of N,N-dimethylformamide in 400 cm3 of 1,2-dichloroethane. The reaction medium is stirred for 3 hours at a temperature in the region of 20° C. and then concentrated under reduced pressure. The residue is dissolved in 150 cm3 of 1,2-dichloroethane and added to a solution of 27.4 g of (R)-2-phenylglycinol while the temperature of the reaction medium is maintained below 10° C. The reaction mixture is stirred for 12 hours at a temperature in the region of 20° C., and is then washed successively with 1000 cm3 of distilled water, 500 cm3 of normal aqueous hydrochloric acid solution, twice 500 cm3 of distilled water and 500 cm3 of saturated aqueous sodium chloride solution. The organic phase is dried over magnesium sulphate and concentrated under reduced pressure. The two diastereoisomers obtained are separated by chromatography on silica [eluent: methylene chloride/ethyl acetate (70:30 by volume)]. The fractions containing each of the two diastereoisomers are pooled and concentrated under reduced pressure. 21.0 g of (R)-2-(3-nitrophenyl)-N-[(R)-2-hydroxy-1-phenylethyl]propionamide (first elution product), melting point 135° C., and 19.0 g of (S)-2-(3-nitrophenyl)-N-[(R) -2-hydroxy-1-phenylethyl]propionamide (second elution product), melting point 150° C., are thereby obtained.

Workup

  1. concentrationconcentrated under reduced pressure
  2. dissolutionThe residue is dissolved in 150 cm3 of 1,2-dichloroethane
  3. additionadded to a solution of 27.4 g of (R)-2-phenylglycinol while the temperature of the reaction medium
  4. temperatureis maintained below 10° C
  5. stirringThe reaction mixture is stirred for 12 hours at a temperature in the region of 20° C.
  6. washis then washed successively with 1000 cm3 of distilled water, 500 cm3 of normal aqueous hydrochloric acid solution, twice 500 cm3 of distilled water and 500 cm3 of saturated aqueous sodium chloride solution
  7. dry with materialThe organic phase is dried over magnesium sulphate
  8. concentrationconcentrated under reduced pressure
  9. customThe two diastereoisomers obtained
  10. customare separated by chromatography on silica [eluent: methylene chloride/ethyl acetate (70:30 by volume)]
  11. additionThe fractions containing each of the two diastereoisomers
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-0f5bd1f2be12455f9b2c6ff257a5ac8c
Source dataset
uspto-grants-1997_05
Patent number
US05633270

Reaction notes

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