Triphenyl phosphite → 10-Oxo-1,3,4,9,10,10a-hexahydro-2,4-a,5,9-tetraaza-phenanthrene-2,7-dicarboxylic acid 2-tert-butyl ester 7-methyl ester

HRID 1644976

Reaktionsgleichung

Reaktionsgleichung von HRID 1644976
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][NH:11][CH:10]([C:14]([OH:16])=O)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].Cl[C:18]1[C:27]([N+:28]([O-])=O)=[CH:26][C:21]([C:22]([O:24][CH3:25])=[O:23])=[CH:20][N:19]=1.C([O-])([O-])=O.[K+].[K+].P(OC1C=CC=CC=1)(OC1C=CC=CC=1)OC1C=CC=CC=1.[H][H]>C1COCC1.C(Cl)Cl.N.O[V](=O)=O.[Pt]>[CH3:25][O:24][C:22]([C:21]1[CH:26]=[C:27]2[C:18]([N:11]3[CH:10]([C:14](=[O:16])[NH:28]2)[CH2:9][N:8]([C:6]([O:5][C:1]([CH3:2])([CH3:3])[CH3:4])=[O:7])[CH2:13][CH2:12]3)=[N:19][CH:20]=1)=[O:23]

Komponenten

10

Edukt 5

HCID 7540Triphenyl phosphiteHCID 11430Potassium CarbonateHCID 346961Methyl 6-chloro-5-nitronicotinateHCID 51758554-[(Tert-butoxy)carbonyl]piperazine-2-carboxylic acidHCID 178418361HCID 178418361, Verbindung

Produkt 1

HCID 5832446410-Oxo-1,3,4,9,10,10a-hexahydro-2,4-a,5,9-tetraaza-phenanthrene-2,7-dicarboxylic acid 2-tert-butyl ester 7-methyl ester

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 23939PlatinumKatalysatorHCID 62684Ammonium metavanadate [UN2859] [Poison]KatalysatorHCID 6344DichloromethaneLösungsmittelHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

To a suspension of 4-(tert-butoxycarbonyl)piperazine-2-carboxylic acid (1169 mg, 5.08 mmol) in THF (46 mL) was added methyl 6-chloro-5-nitronicotinate (1000 mg, 4.62 mmol) and K2CO3 (638 mg, 4.62 mmol). The suspension was heated to reflux for 2 hours, cooled to room temperature, and filtered through a pad of celite. The celite was washed with DCM (50 mL) and the organic portions were combined. The solution was charged into a bomb hydroginator, then treated with triphenyl phosphite (0.015 ml, 0.048 mmol), ammonium vanadate (44 mg, 0.380 mmol), and platinum (1.853 g, 0.475 mmol). The reaction was sealed and pressurized with hydrogen gas (150 psi) overnight. The reaction was then diluted with DCM (100 mL) and heated to reflux for 1 hr. The hot mixture was filtered through celite, washed with DCM (50 mL), and concentrated to 1.65 g (96%) of the title compound as an off-white solid. [M+H] calc'd for C17H22N4O5, 363. found, 363.

Aufarbeitung

  1. temperatureThe suspension was heated
  2. temperatureto reflux for 2 hours
  3. filtrationfiltered through a pad of celite
  4. washThe celite was washed with DCM (50 mL)
  5. additionThe solution was charged into a bomb hydroginator
  6. customThe reaction was sealed
  7. temperatureheated
  8. temperatureto reflux for 1 hr
  9. filtrationThe hot mixture was filtered through celite
  10. washwashed with DCM (50 mL)
  11. concentrationconcentrated to 1.65 g (96%) of the title compound as an off-white solid

Quellen und Nachweise

ORD-Eintrag
ord-5d59ece3366f4319bc63170d60704d90
Quelldatensatz
uspto-grants-2012_02
Patentnummer
US08124606B2

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