2-{[(Benzyloxy)carbonyl]oxy}-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione → HCID 53883501, compound

HRID 745906Notes

Reaction equation

HRID 745906 reaction equation
C(=O)(O)[O-].[Na+].Cl.[OH:7][CH:8]([CH2:16][NH2:17])[CH2:9][CH2:10][C@@H:11]([C:13]([OH:15])=[O:14])[NH2:12].[CH2:18]([O:25][C:26](ON1C(=O)C2C(C3CC2C=C3)C1=O)=[O:27])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1>O.C(#N)C>[CH2:18]([O:25][C:26]([NH:12][C@H:11]([C:13]([OH:15])=[O:14])[CH2:10][CH2:9][CH:8]([OH:7])[CH2:16][NH2:17])=[O:27])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1

Participants

6

Reactant 3

HCID 939132-{[(Benzyloxy)carbonyl]oxy}-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dioneHCID 516892Sodium BicarbonateHCID 22828543HCID 22828543, compound

Product 1

HCID 53883501HCID 53883501, compoundYield 33.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent2×

Procedure

Sodium bicarbonate (4.2 g, 0.050 mol) and 5-hydroxylysine hydrochloride (2.50 g, 0.0126 mol) were dissolved in water (70 ml) with stirring at room temperature. Acetonitrile (40 ml) was added, followed by N-benzyloxycarbonyloxy-5-norbornen-2,3-dicarboximide (3.94 g, 0.0126 mol) in acetonitrile (30 ml) over 15 minutes. After 2 hours, most of the acetonitrile was removed in vacuo and the remaining solution was treated with hydrochloric acid to reduce the pH to 2.0. The solution was extracted with ethyl acetate (50 ml), the pH was increased to 5.5 with sodium hydroxide, and the product was purified over Dowex 50W-2X. The product was eluted with 3% pyridine in water, concentrated to a small volume and freeze dried to give III (1.24 g, 0.0042 mol, 33%); nmr (0.5 M NaOD in D2O)δ 1.4-2.1 (m, 4H, --CH2CH2 --), 3.1-3.5 (m, 2H, --NCH2CH ), 3.5-3.9 (m, 1H, --NCHRCO), 3.9-4.2 (m, 1H, --CH2CHOHCH2 --), 5.10 (s, 2H, --CH2O), 7.39 (s, 5H, --CH2O); mass spectrum (FAB): 297 (M+1).

Workup

  1. custommost of the acetonitrile was removed in vacuo
  2. additionthe remaining solution was treated with hydrochloric acid
  3. extractionThe solution was extracted with ethyl acetate (50 ml)
  4. temperaturethe pH was increased to 5.5 with sodium hydroxide
  5. customthe product was purified over Dowex 50W-2X
  6. washThe product was eluted with 3% pyridine in water
  7. concentrationconcentrated to a small volume and freeze
  8. customdried

Sources & evidence

ORD record
ord-8db4efba152645bbbab7dbd021fb4269
Source dataset
uspto-grants-1986_07
Patent number
US04602002

Reaction notes

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