Phenyl chloroformate → HCID 23153323, compound

HRID 492703Notes

Reaction equation

HRID 492703 reaction equation
[NH2:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][C:7]2[CH:12]=[CH:11][N:10]=[C:9]([NH2:13])[CH:8]=2)=[CH:4][C:3]=1[Cl:16].Cl[C:18](OC1C=CC=CC=1)=[O:19].[CH2:27]([N:29]([CH2:34][CH3:35])[CH2:30][CH2:31][CH2:32][NH2:33])[CH3:28].C(=O)([O-])O.[Na+]>O1CCCC1.O.C(OCC)(=O)C.CN(C)C=O.C(N(CC)CC)C>[NH2:1][C:2]1[CH:15]=[CH:14][C:5]([O:6][C:7]2[CH:12]=[CH:11][N:10]=[C:9]([NH:13][C:18]([NH:33][CH2:32][CH2:31][CH2:30][N:29]([CH2:34][CH3:35])[CH2:27][CH3:28])=[O:19])[CH:8]=2)=[CH:4][C:3]=1[Cl:16]

Participants

10

Reactant 4

HCID 15891Phenyl chloroformate3×HCID 61011N,N-Diethyl-1,3-propanediamineHCID 516892Sodium BicarbonateHCID 229367984-(4-Amino-3-chlorophenoxy)pyridin-2-ylamine

Product 1

HCID 23153323HCID 23153323, compoundYield 51.9%

Reagents, catalysts & solvents 5

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8471TriethylamineSolvent3×HCID 8857Ethyl AcetateSolvent

Procedure

4-(4-Amino-3-chlorophenoxy)pyridin-2-ylamine (750 mg, 3.18 mmol) was dissolved in tetrahydrofuran (30 ml), and then triethylamine (0.444 ml, 4.77 mmol) was added thereto. Phenyl chloroformate (0.399 ml, 4.77 mmol) was added dropwise thereto while ice-cooling, followed by stirring at room temperature for 5 hrs. Triethylamine (0.222 ml) and phenyl chloroformate (0.200 ml) were further added thereto, followed by stirring for 40 min. Triethylamine (0.111 ml) and phenyl chloroformate (0.100 ml) were further added thereto, followed by stirring for 30 min. The reaction mixture was concentrated under a reduced pressure to give a residue, to which N,N-dimethylformamide (10 ml) and 3-(diethylamino)propylamine (2.49 ml, 15.9 mmol) were added, followed by stirring at room temperature for 3 hrs. To the reaction mixture were added ethyl acetate (50 ml) and water (20 ml), and further added a saturated aqueous solution of sodium hydrogencarbonate to partition. The organic layer was washed with brine, and dried over anhydrous sodium sulfate. The solvent was evaporated to give a residue, which was then dried in vacuum to provide the titled compound (645 mg, 1.65 mmol, 51.8%) as a pale yellow solid.

Workup

  1. temperaturewhile ice-cooling
  2. stirringby stirring for 40 min
  3. stirringby stirring for 30 min
  4. concentrationThe reaction mixture was concentrated under a reduced pressure
  5. customto give a residue
  6. stirringby stirring at room temperature for 3 hrs
  7. customto partition
  8. washThe organic layer was washed with brine
  9. dry with materialdried over anhydrous sodium sulfate
  10. customThe solvent was evaporated
  11. customto give a residue, which
  12. customwas then dried in vacuum

Sources & evidence

ORD record
ord-4651915b46344c98af2bc735c6475f33
Source dataset
uspto-grants-2009_05
Patent number
US07531532B2

Reaction notes

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