N-(tert-Butoxycarbonyl)-1,2-phenylenediamine → HCID 68406951, compound

HRID 888013Notes

Reaction equation

HRID 888013 reaction equation
C(OC([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[CH:22]=[CH:21][C:17]([C:18]([OH:20])=O)=[CH:16][CH:15]=2)[CH2:10][CH2:9]1)=O)(C)(C)C.C(OC([NH:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][C:32]=1[NH2:37])=O)(C)(C)C>CN(C=O)C>[NH2:30][C:31]1[CH:36]=[CH:35][CH:34]=[CH:33][C:32]=1[NH:37][C:18](=[O:20])[C:17]1[CH:16]=[CH:15][C:14]([N:11]2[CH2:10][CH2:9][NH:8][CH2:13][CH2:12]2)=[CH:22][CH:21]=1

Participants

4

Reactant 2

HCID 676311N-(tert-Butoxycarbonyl)-1,2-phenylenediamineHCID 27955084-[4-(tert-Butoxycarbonyl)piperazin-1-yl]benzoic acid

Product 1

HCID 68406951HCID 68406951, compoundYield 92%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-(4-t-butoxycarbonylpiperazin-1-yl)benzoic acid (1.0 g, 3.3 mmol) and 1-(t-butoxycarbonylamino)-2-aminobenzene (Method 17, 0.68 g, 3.3 mmol) in DMF (10 ml) was added 4-(4,6-dimethoxy-1,3,5-triazinyl-2-yl)-4-methylmorpholinium chloride (1.1 g, 4.0 mmol) (Method 18). The mixture was stirred at ambient temperature for 20 hours. The mixture was concentrated in vacuo and the residue partitioned between water and ethyl acetate. The organic phase was separated and the aqueous reextracted with ethyl acetate. The combined organic extracts were dried over magnesium sulfate and evaporated. The residue was purified by flash chromatography (eluting with 4:1-1:1 isohexane/ethyl acetate). The product was dissolved in 1,4-dioxane (2.5 ml) and treated with a 4M solution of hydrogen chloride in 1,4-dioxane (2.5 ml). The mixture was stirred at ambient temperature for 4 hours. The resulting solid was collected by filtration, trated with a 2M aqueous solution of sodium hydroxide and extracted with ethyl acetate. The organic extract was dried over magnesium sulfate to afford the title compound as a colourless solid (176 mg, 92%); NMR Spectrum: (DMSO-d6) 2.89 (t, 4H), 3.25 (t, 4H), 4.90 (s, 2H), 6.66 (t, 1H), 6.84 (d, 1H), 7.01 (m, 3H), 7.21 (d, 1H), 7.92 (d, 2H), 9.48 (s, 1H); Mass Spectrum: M+H+ 297.

Workup

  1. concentrationThe mixture was concentrated in vacuo
  2. customthe residue partitioned between water and ethyl acetate
  3. customThe organic phase was separated
  4. dry with materialThe combined organic extracts were dried over magnesium sulfate
  5. customevaporated
  6. customThe residue was purified by flash chromatography (eluting with 4:1-1:1 isohexane/ethyl acetate)
  7. dissolutionThe product was dissolved in 1,4-dioxane (2.5 ml)
  8. additiontreated with a 4M solution of hydrogen chloride in 1,4-dioxane (2.5 ml)
  9. stirringThe mixture was stirred at ambient temperature for 4 hours
  10. filtrationThe resulting solid was collected by filtration
  11. extractionextracted with ethyl acetate
  12. extractionThe organic extract
  13. dry with materialwas dried over magnesium sulfate

Sources & evidence

ORD record
ord-570fdc2004584f8296ca1eac5e52d32e
Source dataset
uspto-grants-2012_08
Patent number
US08247562B2

Reaction notes

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