Ethylmorpholine → methyl N-(tert-butoxycarbonyl)glycylglycinate

HRID 838876Notes

Reaction equation

HRID 838876 reaction equation
C1(N=C=NC2CCCCC2)CCCCC1.[C:16]([O:20][C:21]([NH:23][CH2:24][C:25]([OH:27])=O)=[O:22])([CH3:19])([CH3:18])[CH3:17].ON1C2C=CC=CC=2N=N1.Cl.[CH3:39][O:40][C:41](=[O:44])[CH2:42][NH2:43].C(N1CCOCC1)C>CN(C)C=O>[CH3:39][O:40][C:41](=[O:44])[CH2:42][NH:43][C:25](=[O:27])[CH2:24][NH:23][C:21]([O:20][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:22]

Participants

7

Conditions

Temperature
0 °C

Procedure

Dicyclohexylcarbodiimide (47.46 g, 0.23 mole) is added to a cooled (0° C), stirred solution of t-butoxycarbonyl-glycine (35.6 g, 0.2 mole) and 1-hydroxybenzotriazole (27.03 g, 0.2 mole) in dimethylformamide (400 ml). The mixture is stirred for 1 hour at 0° C and 1 hour at room temperature. A solution of glycine methyl ester hydrochloride (26.4 g, 0.21 mole) and N-ethylmorpholine (52.5 ml, pH 8) in dimethylformamide (1000 ml) is added to above mixture and the mixture is stirred overnight at room temperature. The mixture is filtered and the filtrate is evaporated. The residue is dissolved in ethyl acetate and the solution is washed with 10% citric acid (3×200 ml), saturated sodium bicarbonate (3×270 ml) and brine (2×135 ml), dried over anhydrous magnesium sulfate and evaporated to give t-butoxycarbonylglycyl-glycine methyl ester. To a cooled (0° C) solution of the latter compound (28.6 g, 0.12 mole) in methanol ( 200 ml) is added dropwise IN sodium hydroxide (120 ml). The mixture is stirred for 2 hours at room temperature, cooled to 0° C and acidified with 50% citric acid to pH 4. The solution is evaporated to about one-half volume and the mixture is extracted with ethyl acetate. The organic extract is washed with water and brine, dried over anhydrous magnesium sulfate and evaporated. The residue is crystallized from ethyl acetate to give t-butoxycarbonyl-glycyl-glycine, mp 134°-136° C.

Workup

  1. stirringthe mixture is stirred overnight at room temperature
  2. filtrationThe mixture is filtered
  3. customthe filtrate is evaporated
  4. dissolutionThe residue is dissolved in ethyl acetate
  5. washthe solution is washed with 10% citric acid (3×200 ml), saturated sodium bicarbonate (3×270 ml) and brine (2×135 ml)
  6. dry with materialdried over anhydrous magnesium sulfate
  7. customevaporated

Sources & evidence

ORD record
ord-aa1f5ba127b64d0b9069802b340ee0c7
Source dataset
uspto-grants-1978_06
Patent number
US04093610

Reaction notes

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