Triethylamine → Allyl-N-(tert-butoxycarbonyl)-O-[(4-nitrophenoxy)carbonyl]-L-tyrosinate

HRID 630649Notes

Reaction equation

HRID 630649 reaction equation
[CH2:1]([O:4][C:5](=[O:23])[C@H:6]([CH2:15][C:16]1[CH:21]=[CH:20][C:19]([OH:22])=[CH:18][CH:17]=1)[NH:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH:2]=[CH2:3].Cl[C:25]([O:27][C:28]1[CH:33]=[CH:32][C:31]([N+:34]([O-:36])=[O:35])=[CH:30][CH:29]=1)=[O:26].C(N(CC)CC)C>CN(C)C1C=CN=CC=1.ClCCl>[CH2:1]([O:4][C:5](=[O:23])[C@H:6]([CH2:15][C:16]1[CH:17]=[CH:18][C:19]([O:22][C:25]([O:27][C:28]2[CH:29]=[CH:30][C:31]([N+:34]([O-:36])=[O:35])=[CH:32][CH:33]=2)=[O:26])=[CH:20][CH:21]=1)[NH:7][C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH:2]=[CH2:3]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 821294-Nitrophenyl chloroformateHCID 14769185N-Boc-L-tyrosine allyl ester

Product 1

HCID 117612078Allyl-N-(tert-butoxycarbonyl)-O-[(4-nitrophenoxy)carbonyl]-L-tyrosinate

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent

Procedure

36.7 g (114.3 mmol) N-Boc-L-tyrosine allyl ester, 23.0 g (114.3 mmol) 4-nitrophenyl chloroformate, 17.5 ml (125.7 mmol) triethylamine and 1.40 g (11.4 mmol) 4-dimethylamino pyridine were combined in 1000 ml dichloromethane and stirred at room temperature for 2 h. The reaction mixture was extracted with approx. 500 ml water and with approx. 250 ml brine and dried over approx. 100 g sodium sulfate. The solvent was removed by rotary evaporation (approx. 40° C., approx. 200 mbar, approx. 30 min.) and the product was dissolved in warm diethyl ether and crystallized over night at 4° C. The crystals were filtered of, washed with cold diethyl ether and dried in high vacuum (approx. 0.1 mbar, 18 h). The yield was 29.86 g, (59.6 mmol, 52% of theory) of the desired product.

Workup

  1. extractionThe reaction mixture was extracted with approx. 500 ml water and with approx. 250 ml brine
  2. dry with materialdried over approx. 100 g sodium sulfate
  3. customThe solvent was removed by rotary evaporation (approx. 40° C., approx. 200 mbar, approx. 30 min.)
  4. dissolutionthe product was dissolved in warm diethyl ether
  5. customcrystallized over night at 4° C
  6. filtrationThe crystals were filtered of,
  7. washwashed with cold diethyl ether
  8. customdried in high vacuum (approx. 0.1 mbar, 18 h)

Sources & evidence

ORD record
ord-632a31301d70400191779b0e1b3aa170
Source dataset
uspto-grants-2016_04
Patent number
US09315543B2

Reaction notes

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