Hydrochloric Acid → HCID 60015351, Verbindung

HRID 1429757Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1429757
[CH3:1][CH2:2][C:3]1[CH2:22][N:20]2[CH2:21][C@@H:5]([CH2:6][C@:7]([C:56]([O:58][CH3:59])=[O:57])([C:23]3[CH:24]=[C:25]4[C@:33]56[C@@H:37]7[C@:38]([CH2:53][CH3:54])([C@@H:42]([O:49][C:50]([CH3:52])=[O:51])[C@:43]([OH:48])([C:44]([O:46][CH3:47])=[O:45])[C@@H:32]5[N:31]([CH3:55])[C:26]4=[CH:27][C:28]=3[O:29][CH3:30])[CH:39]=[CH:40][CH2:41][N:36]7[CH2:35][CH2:34]6)[C:8]3[NH:16][C:15]4[CH:14]=[CH:13][C:12]([Br:17])=[CH:11][C:10]=4[C:9]=3[CH2:18][CH2:19]2)[CH:4]=1.Cl.C(C[OH:66])(F)(F)F.[BH4-].[Na+]>O.O.O.O.O.O.O.C([O-])(=O)C([O-])=O.[Fe+3].C([O-])(=O)C([O-])=O.C([O-])(=O)C([O-])=O.[Fe+3].CCOC(C)=O.CO.CCN(CC)CC>[CH3:1][CH2:2][C@@:3]1([OH:66])[CH2:22][N:20]2[CH2:21][C@@H:5]([CH2:6][C@:7]([C:56]([O:58][CH3:59])=[O:57])([C:23]3[CH:24]=[C:25]4[C@:33]56[C@@H:37]7[C@:38]([CH2:53][CH3:54])([C@@H:42]([O:49][C:50]([CH3:52])=[O:51])[C@:43]([OH:48])([C:44]([O:46][CH3:47])=[O:45])[C@@H:32]5[N:31]([CH3:55])[C:26]4=[CH:27][C:28]=3[O:29][CH3:30])[CH:39]=[CH:40][CH2:41][N:36]7[CH2:35][CH2:34]6)[C:8]3[NH:16][C:15]4[CH:14]=[CH:13][C:12]([Br:17])=[CH:11][C:10]=4[C:9]=3[CH2:18][CH2:19]2)[CH2:4]1

Komponenten

10

Edukt 4

HCID 313Hydrochloric AcidHCID 64092,2,2-TrifluoroethanolHCID 4311764Sodium borohydrideHCID 5890524110'-Bromoanhydrovinblastine

Produkt 1

HCID 60015351HCID 60015351, VerbindungAusbeute 22 %

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 57370413Iron(3+) ethanedioate--water (2/3/6)KatalysatorHCID 887MethanolLösungsmittelHCID 962WaterLösungsmittel3×HCID 8471TriethylamineLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A mixture of iron(III) oxalate hexahydrate (148.2 mg, 0.31 mmol, 30 equiv) in H2O (41 mL) was cooled to 0° C. and air was bubbled through the mixture for 10 minutes. A solution of 10′-bromoanhydro-vinblastine (17a, 8.9 mg, 0.010 mmol, 1 equiv) in H2O (0.5 mL), aqueous 0.1 N HCl (0.5 mL), and CF3CH2OH (0.1 mL) was transferred by pipette to the mixture and NaBH4 (7.7 mg, 0.20 mmol, 20 equiv) in H2O (1 mL) was added to the mixture at 0° C. The resulting mixture was stirred for 30 minutes before being quenched by addition of 28-30% aqueous NH4OH (10 mL). The mixture was extracted with 10% MeOH in CH2Cl2 and the organic layer was dried over Na2SO4 and concentrated under reduced pressure. PTLC (SiO2, Et3N:MeOH:EtOAc=3:3:97) provided 10′-bromo-vinblastine (17b, 2.0 mg, 0.0022 mmol, 22%) and 10′-bromoleurosidine (1.3 mg, 0.0015 mmol, 14%).

Aufarbeitung

  1. customair was bubbled through the mixture for 10 minutes
  2. additionwas added to the mixture at 0° C
  3. custombefore being quenched by addition of 28-30% aqueous NH4OH (10 mL)
  4. extractionThe mixture was extracted with 10% MeOH in CH2Cl2
  5. dry with materialthe organic layer was dried over Na2SO4
  6. concentrationconcentrated under reduced pressure

Quellen und Nachweise

ORD-Eintrag
ord-85fba668392540cb996384d6dfe9e614
Quelldatensatz
uspto-grants-2015_01
Patentnummer
US08940754B2

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