Benzene → L-Aspartic acid, 1,4-bis(phenylmethyl) ester, 4-methylbenzenesulfonate (1:1)

HRID 1448024Notes

Reaction equation

HRID 1448024 reaction equation
[NH2:1][C@H:2]([C:7]([OH:9])=[O:8])[CH2:3][C:4]([OH:6])=[O:5].[CH2:10](O)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.O.[C:19]1([CH3:29])[CH:24]=[CH:23][C:22]([S:25]([OH:28])(=[O:27])=[O:26])=[CH:21][CH:20]=1.C1C=CC=CC=1>O.ClC(Cl)=C(Cl)Cl.C1(C)C=CC=CC=1>[C:19]1([CH3:29])[CH:20]=[CH:21][C:22]([S:25]([OH:28])(=[O:26])=[O:27])=[CH:23][CH:24]=1.[NH2:1][C@H:2]([C:7]([O:9][CH2:29][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)=[O:8])[CH2:3][C:4]([O:6][CH2:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:5]

Participants

8

Reactant 4

HCID 241Benzene2×HCID 244Benzyl AlcoholHCID 5960L-Aspartic AcidHCID 521998p-Toluenesulfonic acid monohydrate

Product 1

HCID 2808531L-Aspartic acid, 1,4-bis(phenylmethyl) ester, 4-methylbenzenesulfonate (1:1)

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1140TolueneSolventHCID 31373TetrachloroethyleneSolvent

Procedure

A stirred mixture of L-aspartic acid (133 g.; 1.00 mole), benzyl alcohol (650 g.; 6.00 moles), p-toluenesulfonic acid monohydrate (194 g.; 1.02 moles), and dry benzene (400 ml.) was heated at reflux for 6.5 hours. Although benzene has been used, it is within the scope of the invention to employ other solvents such as, for example, toluene and tetrachloroethylene. The water formed in the reaction (46 ml.) was removed by means of a Dean-Stark trap. The resulting solution was cooled to room temperature then diluted with benzene (400 ml.) and ether (1200 ml.). On cooling to 10°, a white solid precipitated. This material was collected on a filter, washed with ether (1.0 l.), and dried; yield of crude (I), 384 g. (79%). A 304 g. portion of the product was recrystallized from methanol (425 ml.) to give 186 g. (61.2% recovery) of material suitable for further transformation; m.p., 155.5°-158°; literature m.p., 158°-160° .

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 6.5 hours
  3. customwas removed by means of a Dean-Stark trap
  4. additionthen diluted with benzene (400 ml.) and ether (1200 ml.)
  5. temperatureOn cooling to 10°
  6. customa white solid precipitated
  7. customThis material was collected on a filter
  8. washwashed with ether (1.0 l.)
  9. customdried
  10. customportion of the product was recrystallized from methanol (425 ml.)
  11. customto give 186 g
  12. customm.p., 155.5°-158°
  13. customliterature m.p., 158°-160°

Sources & evidence

ORD record
ord-288905504f0d449b8c301ce93aa51082
Source dataset
uspto-grants-1979_12
Patent number
US04179464

Reaction notes

Loading…