Nitrogen → HCID 23593636, compound

HRID 1243304Notes

Reaction equation

HRID 1243304 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([NH:14][C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=2[S:21][C:22]2[CH:27]=[CH:26][C:25]([Cl:28])=[CH:24][C:23]=2Cl)[CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C(=O)([O-])[O-].[Cs+].[Cs+].N#N>CN(C=O)C.[Cu]I.[Cu]>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][CH2:11][CH:10]([N:14]2[C:27]3[CH:26]=[C:25]([Cl:28])[CH:24]=[CH:23][C:22]=3[S:21][C:16]3[C:15]2=[CH:20][CH:19]=[CH:18][CH:17]=3)[CH2:9]1)=[O:7])([CH3:3])([CH3:2])[CH3:4]

Participants

7

Reactant 3

HCID 947NitrogenHCID 10796Cesium carbonateHCID 23593637HCID 23593637, compound

Product 1

HCID 23593636HCID 23593636, compoundYield 53.2%

Reagents, catalysts & solvents 3

HCID 23978CopperCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 6228DimethylformamideSolvent

Procedure

3-[2-(2,4-Dichlorophenylsulfanyl)phenylamino]piperidine-1-carboxylic acid tert-butyl ester (8.4 g, 18.5 mmol) was dissolved in DMF (120 mL) and vigorously degassed with N2 for 20 min. Cesium carbonate (27.2 g, 83.5 mmol), copper(I) iodide (5.28 g, 27.8 mmol), and copper powder (8.4 g, 132 mmol) were added to the solution. The suspension was stirred vigorously and heated to 155–156° C. for 12 hours (N2 was continuously bubbled through the mixture). The mixture was cooled to room temperature and diluted with ethyl acetate. The solids were removed by vacuum filtration and were rinsed with ethyl acetate. The filtrate was concentrated under vacuum to remove 90% of the volatiles. The residue was purified by SiO2 chromatography to provide 3-(2-chlorophenothiazin-10-yl)piperidine-1-carboxylic acid tert-butyl ester (4.1 g, 53%) as a white solid.

Workup

  1. customvigorously degassed with N2 for 20 min
  2. customwas continuously bubbled through the mixture)
  3. additiondiluted with ethyl acetate
  4. customThe solids were removed by vacuum filtration
  5. washwere rinsed with ethyl acetate
  6. concentrationThe filtrate was concentrated under vacuum
  7. customto remove 90% of the volatiles
  8. customThe residue was purified by SiO2 chromatography

Sources & evidence

ORD record
ord-22068cf2f3f148c09ac37747ab452333
Source dataset
uspto-grants-2006_10
Patent number
US07119089B2

Reaction notes

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