Dicyclohexylcarbodiimide → BOC-(D)-Asn-Gly-MePhe-NHNHCSNH2

HRID 1156951Notes

Reaction equation

HRID 1156951 reaction equation
[NH:1]([C:22]([O:24]C(C)(C)C)=O)[CH2:2][C:3]([N:5]([CH3:21])[C@H:6]([C:14]([NH:16][NH:17][C:18]([NH2:20])=[S:19])=[O:15])[CH2:7][C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)=[O:4].[NH:29]([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[C@@H:30](C(O)=O)[CH2:31][C:32](=[O:34])[NH2:33].C1C2C3C(=O)N(O)C(=O)C3C1C=C2.C1CCC(N=C=NC2CCCCC2)CC1>FC(F)(F)C(O)=O.CN(C=O)C>[NH:29]([C:38]([O:40][C:41]([CH3:44])([CH3:43])[CH3:42])=[O:39])[C@@H:30]([C:22]([NH:1][CH2:2][C:3]([N:5]([CH3:21])[C@H:6]([C:14]([NH:16][NH:17][C:18]([NH2:20])=[S:19])=[O:15])[CH2:7][C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1)=[O:4])=[O:24])[CH2:31][C:32](=[O:34])[NH2:33]

Participants

7

Reactant 4

HCID 10868DicyclohexylcarbodiimideHCID 895293a,4,7,7a-Tetrahydro-2-hydroxy-4,7-methano-1H-isoindole-1,3(2H)-dioneHCID 1623168Boc-D-asparagineHCID 12802635HCID 12802635, compound

Product 1

HCID 12802643BOC-(D)-Asn-Gly-MePhe-NHNHCSNH2

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6422Trifluoroacetic acidSolvent

Procedure

In 10 ml of trifluoroacetic acid is dissolved 0.80 g of BOC-Gly-MePhe-NHNHCSNH2 and the solution is shaken for 10 minutes, concentrated, treated with ether and filtered to obtain a powder. This powder is dissolved in 10 ml of DMF, and after ice-cooling, the solution is neutralized with 0.20 ml of TEA followed by addition of 0.47 g of BOC-(D)-Asn-OH, 0.40 g of HONB and 0.45 g of DCC. The mixture is stirred for 20 hours, the precipitated DCU filtered off, the solvent distilled off and the residue dissolved in n-butanol. The solution is washed with a saturated aqueous solution of sodium hydrogen carbonate and water in that order and dried over anhydrous sodium sulfate. The solvent is distilled off and the residue is treated with ether and filtered to obtain a powder, which is further reprecipitated from methanol-ether. Yield 0.69 g; m.p. 124°-127° C.; [α]D24 -42.5° (c=1.0, DMF); Rf1 0.16.

Workup

  1. concentrationconcentrated
  2. additiontreated with ether
  3. filtrationfiltered
  4. customto obtain a powder
  5. temperatureafter ice-cooling
  6. stirringThe mixture is stirred for 20 hours
  7. filtrationthe precipitated DCU filtered off
  8. distillationthe solvent distilled off
  9. dissolutionthe residue dissolved in n-butanol
  10. washThe solution is washed with a saturated aqueous solution of sodium hydrogen carbonate and water in that order
  11. dry with materialdried over anhydrous sodium sulfate
  12. distillationThe solvent is distilled off
  13. additionthe residue is treated with ether
  14. filtrationfiltered
  15. customto obtain a powder, which
  16. customis further reprecipitated from methanol-ether

Sources & evidence

ORD record
ord-f4fbd834bdee40638a0179a2ed702840
Source dataset
uspto-grants-1982_06
Patent number
US04337247

Reaction notes

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