Acetic Acid → HCID 86682385, compound

HRID 1465834Notes

Reaction equation

HRID 1465834 reaction equation
[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:16]=[C:15]3[C:11]([CH:12]=[C:13]([C:27]4[CH:32]=[CH:31][C:30]([NH2:33])=[C:29]([N+:34]([O-])=O)[CH:28]=4)[N:14]3[S:17]([C:20]3[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=3)(=[O:19])=[O:18])=[CH:10][CH:9]=2)[CH2:4][CH2:3]1.[C:37]([C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][N:40]=1)#N.C[O-].[Na+].C(O)(=O)C>CO.CC(O)=O.[Pd].CO>[CH3:1][N:2]1[CH2:7][CH2:6][N:5]([C:8]2[CH:16]=[C:15]3[C:11]([CH:12]=[C:13]([C:27]4[CH:32]=[CH:31][C:30]5[N:33]=[C:37]([C:39]6[CH:44]=[CH:43][CH:42]=[CH:41][N:40]=6)[NH:34][C:29]=5[CH:28]=4)[N:14]3[S:17]([C:20]3[CH:25]=[CH:24][C:23]([CH3:26])=[CH:22][CH:21]=3)(=[O:19])=[O:18])=[CH:10][CH:9]=2)[CH2:4][CH2:3]1

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 7522Pyridine-2-carbonitrileHCID 10942334Sodium MethoxideHCID 86682384HCID 86682384, compound

Product 1

HCID 86682385HCID 86682385, compoundYield 26.9%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 10129899Acetic acid methanolSolvent

Conditions

Temperature
80 °C

Procedure

The 4-[6-(4-Methyl-piperazin-1-yl)-1-(toluene-4-sulfonyl)-1H-indol-2-yl]-2-nitro-phenylamine (0.5 g, 0.99 mmol), was dissolved in 7:3 MeOH/HOAc (100 ml), and hydrogenated in the presence of 5% palladium on carbon (100 mg), overnight. The solution was then filtered through celite, washed with methanol (50 ml), and evaporated. The resulting diamine was dissolved in methanol (20 ml). To this was added a solution of 2-cyanopyridine (154 mg, 1.5 mmol) that had been treated (immediately before) with sodium methoxide (0.15 mmol) in methanol (2 mL) at 40° C. for 1.5 hour under nitrogen. To this mixture, acetic acid (0.21 ml, 3.8 mmol) was added. This mixture was heated at 80° C. overnight under nitrogen followed by cooling to room temperature, and removing the solvents under reduced pressure. Next the residue treated with a 5% aqueous ammonia solution, incubated at 5° C. over one day, decanted the aqueous layer, washed well with water. Resulting light tan solid was isolated and washed with ether to give the product 150 mg (15% yield). The material while not completely pure, could be taken to next step.

Workup

  1. filtrationThe solution was then filtered through celite
  2. washwashed with methanol (50 ml)
  3. customevaporated
  4. dissolutionThe resulting diamine was dissolved in methanol (20 ml)
  5. temperatureby cooling to room temperature
  6. customremoving the solvents under reduced pressure
  7. additionNext the residue treated with a 5% aqueous ammonia solution
  8. customdecanted the aqueous layer
  9. washwashed well with water
  10. customResulting light tan solid
  11. customwas isolated
  12. washwashed with ether

Sources & evidence

ORD record
ord-ed74b9db37714526990d447658333be5
Source dataset
uspto-grants-2015_04
Patent number
US08999993B2

Reaction notes

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