N-bromobutanimide → HCID 54221950, compound

HRID 2418436Notes

Reaction equation

HRID 2418436 reaction equation
O=[C:2]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][N:18]1[C:22](=[O:23])[C:21]2=[CH:24][CH:25]=[CH:26][CH:27]=[C:20]2[C:19]1=[O:28])[C:3]([O:5]CC1C=CC=CC=1)=[O:4].S1CCCSC1C(OCC1C=CC=CC=1)=O.C1(=O)N(CCCCCBr)C(=O)C2=CC=CC=C12.BrN1C(=O)CCC1=O.[NH2:70][C@H:71]([C:73]([N:75]1[CH2:82][CH2:81][CH2:80][C@H:76]1[C:77]([OH:79])=[O:78])=[O:74])[CH3:72].[BH3-]C#N.[Na+].C(OC(C(N[C@H](C(N1CCC[C@H]1C(O)=O)=O)C)CCCCCN1C(=O)C2=CC=CC=C2C1=O)=O)C1C=CC=CC=1>C(O)C.[Pd]>[C:3]([CH:2]([NH:70][C@H:71]([C:73]([N:75]1[CH2:82][CH2:81][CH2:80][C@H:76]1[C:77]([OH:79])=[O:78])=[O:74])[CH3:72])[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][N:18]1[C:19](=[O:28])[C:20]2=[CH:27][CH:26]=[CH:25][CH:24]=[C:21]2[C:22]1=[O:23])([OH:5])=[O:4]

Participants

10

Reactant 7

HCID 67184N-bromobutanimideHCID 83525L-Alanyl-L-prolineHCID 136770N-(5-Bromopentyl)phthalimideHCID 5003444Sodium cyanoborohydrideHCID 20445876HCID 20445876, compoundHCID 21464099HCID 21464099, compoundHCID 54509736HCID 54509736, compound

Product 1

HCID 54221950HCID 54221950, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

Benzyl 2-oxo-7-phthalimidoheptanoate (prepared by alkylation of benzyl 1,3-dithiane-2-carboxylate with 5-phthalimidopentyl bromide and subsequent oxidative conversion to the ketone with N-bromosuccinimide) is condensed with L-alanyl-L-proline in the presence of excess NaBH3CN. The condensation product, N-(1-benzyloxycarbonyl-6-phthalimidohexyl)-L-alanyl-L-proline, (390 mg.) in 25 ml of 50% aqueous ethanol is hydrogenated at 40 psi over 10% palladium on charcoal. Removal of solvent and catalyst yields N-(1-carboxy-6-phthalimidohexyl)-L-alanyl-L-proline (320 mg) having the expected spectral and chromatographic properties. A portion of the above intermediate (152 mg) in 2 ml of ethanol is refluxed with hydrazine (32 mg) for 1.5 hours. The phthalhydrazide is removed by filtration; the ethanol is removed under vacuum and the residue is absorbed on strong acid ion-exchange resin. Elution with 2% aqueous pyridine and freeze-drying gives the desired N-(1-carboxy-6-aminohexyl)-L-alanyl-L-proline (58 mg.). The spectral data are consistent with structure. The mass spectrum shows a peak at 311 for the molecular ion minus water (329-18).

Workup

  1. customRemoval of solvent and catalyst

Sources & evidence

ORD record
ord-d68d472ba6de48cd8dec66e97521d4bc
Source dataset
uspto-grants-1984_09
Patent number
US04472380

Reaction notes

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