Dimethylformamide → Ammonia

HRID 969300Notes

Reaction equation

HRID 969300 reaction equation
Br[C:2]1[N:7]=[CH:6][C:5]([N:8]2[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]2)=[CH:4][C:3]=1[Cl:21].[CH3:22][Sn](C)(C)C.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CN(C)C=O>Cl.[Pd]>[NH3:7].[Cl:21][C:3]1[CH:4]=[C:5]([N:8]2[CH2:13][CH2:12][N:11]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[CH2:10][CH2:9]2)[CH:6]=[N:7][C:2]=1[CH3:22]

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 11661TetramethyltinHCID 11776TriphenylphosphineHCID 11689360HCID 11689360, compound

Product 2

HCID 222AmmoniaHCID 9836364HCID 9836364, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 313Hydrochloric AcidSolvent

Conditions

Temperature
160 °C

Procedure

A mixture of 1-(6-bromo-5-chloro-3-pyridyl)-4-tert-butoxycarbonyl-piperazine (2.0 g, 5.3 mmol), tetramethyltin (1.9 g, 10.6 mmol), palladium-di-(triphenylphosphine (0.19 g, 0.26 mmol) and dimethylformamide (2 ml) was stirred at 160° C. in a sealed vessel overnight. The mixture was stirred in conc. hydrochloric acid (30 ml) at reflux for 15 min. The mixture was evaporated. Aqueous sodium hydroxide (50 ml, 1 M) was added and the mixture was extracted with dichloromethane (3×50 ml). Chromatography of this crude mixture on silica gel with dichloromethane, methanol and conc. ammonia (89:10:1) gave the title compound. Yield 0.70 g (43%). The corresponding salt was obtained by addition of a diethyl ether and methanol mixture (9:1) saturated with fumaric acid. Mp 178.1-180.5° C.

Workup

  1. temperatureat reflux for 15 min
  2. customThe mixture was evaporated
  3. additionAqueous sodium hydroxide (50 ml, 1 M) was added
  4. extractionthe mixture was extracted with dichloromethane (3×50 ml)

Sources & evidence

ORD record
ord-2aba0a8789ce41b1b89facc4a9464832
Source dataset
uspto-grants-2007_12
Patent number
US07307087B2

Reaction notes

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