Methanol → HCID 178511789, compound

HRID 2288582Notes

Reaction equation

HRID 2288582 reaction equation
C(OC([NH:11][C@H:12]([C:19]([N:21]1[CH2:28][CH2:27][CH2:26][C@H:22]1[C:23]([NH2:25])=[O:24])=[O:20])[CH2:13][C:14]1[N:18]=[CH:17][NH:16][CH:15]=1)=O)C1C=CC=CC=1.C[OH:30].O>[Pd].C(O)(=O)C>[O:24]=[C:23]1[NH:25][CH2:27][CH2:28][NH:21][C:22]1=[O:30].[NH2:11][C@H:12]([C:19]([N:21]1[CH2:28][CH2:27][CH2:26][C@H:22]1[C:23]([OH:24])=[O:30])=[O:20])[CH2:13][C:14]1[N:18]=[CH:17][NH:16][CH:15]=1

Participants

6

Reactant 3

HCID 887MethanolHCID 962WaterHCID 178513961HCID 178513961, compound

Product 1

HCID 178511789HCID 178511789, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolvent

Procedure

Benzyloxycarbonyl-L-histidyl-L-prolineamide (500 mg) was dissolved in a solution containing methanol (10 ml), H2O (0.3 ml) and glacial acetic acid (0.3 ml). After adding palladium black catalyst (100 mg), the suspension was hydrogenated under 40 pounds of pressure for 2 hours. The catalyst was then filtered and the resultant solution was heated in boiling water for 30 minutes, then dried in vacuo. After dissolving the product in water, it was purified by passage through a column (2×5 cm) of diethylaminoethylcellulose and subsequently washed with water. The Pauly positive fractions were concentrated to dryness in vacuo to yield crystalline L-histidyl-L-proline diketopiperazine (yield approximately 200 mg). Elemental analysis showed C, H, N, and O at 54.75%, 6.08%, 22.10% and 17.22% respectively. Theoretical calculated values for C, H, N and O are 53.91%, 6.25%, 22.86% and 16.97% respectively. Mass spectrographic analysis showed prominent ions at m/e 234, m/e 154, m/e 81 and m/e 70. Proton NMR showed chemical shifts at 1.95, 2.2, 3.4, 3.5, 4.65, 7.4, 8.25 ppm downfield from trimethylsilane. Amino acid analysis showed the presence of ninhydrin-positive material corresponding to only proline and histidine with a ratio of 1.1 to 1.

Workup

  1. filtrationThe catalyst was then filtered
  2. temperaturethe resultant solution was heated
  3. customfor 30 minutes
  4. customdried in vacuo
  5. dissolutionAfter dissolving the product in water
  6. customit was purified by passage through a column (2×5 cm) of diethylaminoethylcellulose
  7. washsubsequently washed with water
  8. concentrationThe Pauly positive fractions were concentrated to dryness in vacuo

Sources & evidence

ORD record
ord-14bed29a408d40d180995f6f9f58da13
Source dataset
uspto-grants-2000_07
Patent number
US06090780

Reaction notes

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