1,3-Benzenediamine, 5-chloro- → HCID 90051718, compound

HRID 2284647Notes

Reaction equation

HRID 2284647 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([NH2:9])[CH:5]=[C:6]([NH2:8])[CH:7]=1.[C:10]([NH:17][CH2:18][C:19](O)=[O:20])([O:12][C:13]([CH3:16])([CH3:15])[CH3:14])=[O:11].F[P-](F)(F)(F)(F)F.C(C(=NO[C+](N(C)C)N1CCOCC1)C(OCC)=O)#N.C(=O)([O-])O.[Na+]>CN(C)C=O.CN1CCOCC1.C(OCC)(=O)C>[NH2:8][C:6]1[CH:5]=[C:4]([NH:9][C:19](=[O:20])[CH2:18][NH:17][C:10](=[O:11])[O:12][C:13]([CH3:14])([CH3:15])[CH3:16])[CH:3]=[C:2]([Cl:1])[CH:7]=1

Participants

8

Reactant 4

HCID 733351,3-Benzenediamine, 5-chloro-HCID 78288N-(tert-butoxycarbonyl)glycineHCID 516892Sodium BicarbonateHCID 178472143HCID 178472143, compound

Product 1

HCID 90051718HCID 90051718, compoundYield 31.9%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 79724-MethylmorpholineSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
130 °C

Procedure

To a solution of 5-chloro-1,3-phenylenediamine (1.22 g), N-Boc-glycine (500 mg) and (1-cyano-2-ethoxy-2-oxoethylideneaminoxy)dimethylamino-morpholino-carbenium hexafluorophosphate (1.83 g) in N,N-dimethylformamide (5 mL), N-methylmorpholine (628 μL) was added at room temperature, and the mixture was stirred at 130° C. for 5 hours. The reaction mixture was cooled to room temperature, and then saturated aqueous sodium hydrogencarbonate and ethyl acetate were added to the mixture. The organic layer was separated, and the aqueous layer was extracted with ethyl acetate. The organic layer and the extract were combined, washed successively with water and saturated aqueous sodium chloride, and then dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by basic silica gel column chromatography (eluent, 70 to 40% hexane in ethyl acetate) to obtain tert-butyl (2-((3-amino-5-chlorophenyl)amino)-2-oxoethyl)carbamate (B10, 273 mg) as yellow solid.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted with ethyl acetate
  4. washwashed successively with water and saturated aqueous sodium chloride
  5. dry with materialdried over anhydrous sodium sulfate
  6. customthe solvent was evaporated under reduced pressure
  7. customThe obtained residue was purified by basic silica gel column chromatography (eluent, 70 to 40% hexane in ethyl acetate)

Sources & evidence

ORD record
ord-6b5ff7db48f84161bf25ef5a516dce8d
Source dataset
uspto-grants-2015_09
Patent number
US09145415B2

Reaction notes

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