Acetic Acid → HCID 178480945, Verbindung

HRID 51618

Reaktionsgleichung

Reaktionsgleichung von HRID 51618
[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][N:8]([CH:12]3[CH2:17][CH2:16][C:15](=O)[CH2:14][CH2:13]3)[C:4]=2[N:5]=[CH:6][N:7]=1.[CH3:19][N:20]1[CH2:25][CH2:24][NH:23][CH2:22][CH2:21]1.C(O)(=O)C.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+].C(=O)(O)[O-].[Na+]>O>[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][N:8]([C@H:12]3[CH2:17][CH2:16][C@@H:15]([N:23]4[CH2:24][CH2:25][N:20]([CH3:19])[CH2:21][CH2:22]4)[CH2:14][CH2:13]3)[C:4]=2[N:5]=[CH:6][N:7]=1.[Cl:1][C:2]1[C:3]2[C:10]([I:11])=[CH:9][N:8]([C@H:12]3[CH2:17][CH2:16][C@H:15]([N:23]4[CH2:24][CH2:25][N:20]([CH3:19])[CH2:21][CH2:22]4)[CH2:14][CH2:13]3)[C:4]=2[N:5]=[CH:6][N:7]=1

Komponenten

8

Edukt 5

HCID 176Acetic AcidHCID 531671-MethylpiperazineHCID 516892Sodium BicarbonateHCID 5049666Sodium triacetoxyborohydrideHCID 227364134-(4-Chloro-5-iodo-pyrrolo[2,3-d]pyrimidin-7-yl)-cyclohexanone

Produkt 2

HCID 178480945HCID 178480945, VerbindungAusbeute 42 %HCID 178480946HCID 178480946, Verbindung

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 962WaterLösungsmittel

Versuchsvorschrift

A mixture of 4-(4-chloro-5-iodo-7H-pyrrolo[2,3-d]pyrimidin-7-yl)-1-cyclohexanone (20.0 g, 53.3 mmol), 1-methylpiperazine (6.42 g, 128 mmol) and acetic acid (7.7 g, 128 mmol) in 1,2-dichloromethane (1 L) was stirred for 15 minutes at ambient temperature. Sodium triacetoxyborohydride (14.7 g, 69.3 mmol) was added and stirring was continued for 20 hours. Water (400 mL) was added followed by sodium bicarbonate (26.0 g, 310 mmol). The mixture was transferred to a separatory funnel and the layers separated. The aqueous layer was extracted with dichloromethane (300 mL). The combined organic extracts were dried over magnesium sulfate, filtered and the filtrate concentrated under reduced pressure. The resulting oil was purified by flash chromatography on silica gel (275 g) using dichloromethane/methanol (9:1) as an eluent to give cis-4-chloro-5-iodo-7-[4-(4-methylpiperazino)cyclohexyl]-7H-pyrrolo[2,3-d]pyrimidine (10.2 g, 42%) and trans-4-chloro-5-iodo-7-[4-(4-methylpiperazino)cyclohexyl]-7H-pyrrolo[2,3-d]pyrimidine (5.8 g) which contained 10% of the cis isomer. This mixture was stirred in diethyl ether (100 mL) for 1.5 hours then the solid was collected by filtration to provide pure trans-4-chloro-5-iodo-7-[4-(4-methylpiperazino)cyclohexyl]-7H-pyrrolo[2,3-d]pyrimidine (5.0 g, 20.2%).

Aufarbeitung

  1. stirringstirring
  2. waitwas continued for 20 hours
  3. customThe mixture was transferred to a separatory funnel
  4. customthe layers separated
  5. extractionThe aqueous layer was extracted with dichloromethane (300 mL)
  6. dry with materialThe combined organic extracts were dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationthe filtrate concentrated under reduced pressure
  9. customThe resulting oil was purified by flash chromatography on silica gel (275 g)

Quellen und Nachweise

ORD-Eintrag
ord-54670ea514ad41b89bedfd67f85b208a
Quelldatensatz
uspto-grants-2004_03
Patentnummer
US06713474B2

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