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

HRID 1448025Notes

Reaction equation

HRID 1448025 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>[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

6

Reactant 4

HCID 241BenzeneHCID 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 1

HCID 962WaterSolvent

Procedure

A stirred mixture of L-aspartic acid (399 g.; 3.00 moles), benzyl alcohol (1.95 kg.; 18.0 moles), p-toluenesulfonic acid monohydrate (582 g.; 3.06 moles), and dry benzene (1.2 l.) was heated at reflux for 16 hours. The water formed in the reaction (145 ml.) was removed by means of a Dean-Stark trap. The resulting solution was cooled to room temperature, then diluted with benzene (1.2 l.) and ether (3.6 l.). The resulting solid was collected on a filter, washed with ether (7.0 l.), and dried; yield, 1195 g. (82%). The crude product was recrystallized from methanol (1720 ml.) to give 959 g. (80% recovery) of purified (I); m.p., 158°-159.5°; literature m.p., 158°-160°. Additional reactions were carried out to give a total of 4.27 kg. of product suitable for further transformation.

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 16 hours
  3. customwas removed by means of a Dean-Stark trap
  4. additiondiluted with benzene (1.2 l.) and ether (3.6 l.)
  5. customThe resulting solid was collected on a filter
  6. washwashed with ether (7.0 l.)
  7. customdried
  8. customyield
  9. customThe crude product was recrystallized from methanol (1720 ml.)
  10. customto give 959 g
  11. custom(80% recovery) of purified (I)
  12. customm.p., 158°-159.5°
  13. customliterature m.p., 158°-160°
  14. customto give a total of 4.27 kg

Sources & evidence

ORD record
ord-dd9cb1596fd543c992d617a237b4c78b
Source dataset
uspto-grants-1979_12
Patent number
US04179464

Reaction notes

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