Ethylmorpholine → HCID 13341543, compound

HRID 542618Notes

Reaction equation

HRID 542618 reaction equation
C([C:4]1[CH:31]=[C:8]2[C:9]([N:11]([CH:14]([CH2:29][CH3:30])[C:15]([N:17]3[CH:21]([C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])[CH2:20][CH2:19][NH:18]3)=[O:16])[C:12](=[O:13])[C:7]2=[CH:6][CH:5]=1)=[O:10])(O)=O.C(N1CC[O:37][CH2:36]C1)C.P(Cl)(Cl)(Cl)(Cl)Cl>O1CCCC1>[O:37]=[C:36]1[CH2:30][CH2:29][C@H:14]([N:11]2[C:12](=[O:13])[C:7]3=[CH:6][CH:5]=[CH:4][CH:31]=[C:8]3[C:9]2=[O:10])[C:15](=[O:16])[N:17]2[C@H:21]([C:22]([O:24][C:25]([CH3:26])([CH3:28])[CH3:27])=[O:23])[CH2:20][CH2:19][N:18]12

Participants

5

Reactant 3

HCID 7525Ethylmorpholine3×HCID 24819Phosphorus pentachloride2×HCID 70393761HCID 70393761, compound

Product 1

HCID 13341543HCID 13341543, compoundYield 33.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A stirred solution of 3.45 g of the tert.butyl 2-(5-carboxy-2-phthalimidobutyryl)-3-pyrazolidinecarboxylate and 0.92 g of N-ethylmorpholine in 50 ml of dry tetrahydrofuran was cooled to 0° C. and treated with 1.66 g of phosphorus pentachloride. After 1 hour, a further 0.92 g of N-ethylmorpholine and 1.66 g of phosphorus pentachloride were added and, after a further 1 hour, another 0.92 g of N-ethylmorpholine was added. The solvent was removed by evaporation and the residue was partitioned between water and ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate solution, dried over magnesium sulphate and evaporated. The oil obtained was chromatographed on silica gel. Elution with diethyl ether yielded firstly 1.1 g (33%) of tert.butyl 2,3,6,7,8,9-hexahydro-5,9-dioxo-8(S)-phthalimido-1H,5H-pyrazolo[1,2-α][1,2]diazepine-1(S)-carboxylate in the form of a white foam and then 0.52 g (15%) of tert.butyl 2,3,6,7,8,9-hexahydro-5,9-dioxo-8(S)-phthalimido-1H,5H-pyrazolo[1,2-a][1,2]diazepine-1(R)-carboxylate in the form of a white solid of melting point 180°-181° C. (from ethyl acetate/n-hexane).

Workup

  1. customThe solvent was removed by evaporation
  2. customthe residue was partitioned between water and ethyl acetate
  3. washThe organic layer was washed with saturated aqueous sodium bicarbonate solution
  4. dry with materialdried over magnesium sulphate
  5. customevaporated
  6. customThe oil obtained
  7. customwas chromatographed on silica gel
  8. washElution with diethyl ether

Sources & evidence

ORD record
ord-5cc24b184bbb4ed3b19468b09c42da7f
Source dataset
uspto-grants-1987_04
Patent number
US04658024

Reaction notes

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