Chloroacetyl chloride → HCID 54439852, compound

HRID 1885418Notes

Reaction equation

HRID 1885418 reaction equation
C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH2:12]([O:19][C:20](=[O:34])[C@H:21]([CH2:23][C:24]([O:26][CH2:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)=[O:25])[NH2:22])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.C(N(CC)CC)C.[Cl:42][CH2:43][C:44](Cl)=[O:45]>C(OCC)(=O)C>[CH2:12]([O:19][C:20](=[O:34])[C@H:21]([CH2:23][C:24]([O:26][CH2:27][C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)=[O:25])[NH:22][C:44](=[O:45])[CH2:43][Cl:42])[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

5

Reactant 3

HCID 6577Chloroacetyl chlorideHCID 8471TriethylamineHCID 2808531L-Aspartic acid, 1,4-bis(phenylmethyl) ester, 4-methylbenzenesulfonate (1:1)

Product 1

HCID 54439852HCID 54439852, compoundYield 96%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A solution of L-aspartic acid dibenzyl ester p-toluene sulfonic acid salt (150 g, 0.309 mol) and distilled triethylamine (93 mL, 0.67 mol) in ethyl acetate (1.1 L) was cooled to 0° C. Chloroacetyl chloride (25.5 mL, 0.32 mol) was added to the resulting solution at a rate such that the reaction temperature did not exceed 10° C. The reaction mixture was then stirred at room temperature for a period of 1.5 hours. The resulting heterogeneous mixture was filtered to remove triethylamine salts. The organic filtrate was sequentially extracted with aqueous 1N HCl (2×250 mL), water (about 300 mL), half-saturated aqueous sodium carbonate (250 mL), water (about 300 mL), and brine (about 300 mL). The organic phase was dried over magnesium sulfate and concentrated in vacuo to provide product 11 (115.6 g, 0.296 mol, 96%) as a viscous brown oil which crystallized on standing. Satisfactory 1H NMR data were obtained for this material. This material was not further purified but was instead used directly in the preparation of iodide 12.

Workup

  1. customdid not exceed 10° C
  2. filtrationThe resulting heterogeneous mixture was filtered
  3. customto remove triethylamine salts
  4. extractionThe organic filtrate was sequentially extracted with aqueous 1N HCl (2×250 mL), water (about 300 mL), half-saturated aqueous sodium carbonate (250 mL), water (about 300 mL), and brine (about 300 mL)
  5. dry with materialThe organic phase was dried over magnesium sulfate
  6. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-f697fd92e0e34666bb98d531193699ab
Source dataset
uspto-grants-1992_09
Patent number
US05144073

Reaction notes

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