1-Chloroethyl chloroformate → HCID 69060680, compound

HRID 2102777Notes

Reaction equation

HRID 2102777 reaction equation
C([N:8]1[CH2:13][CH2:12][N:11]([C:14]2[N:19]=[C:18]3[C:20]([S:23]([C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)(=[O:25])=[O:24])=[CH:21][NH:22][C:17]3=[CH:16][CH:15]=2)[CH2:10][CH2:9]1)C1C=CC=CC=1.[Cl:32]C(OC(Cl)=O)C>ClCCCl>[ClH:32].[ClH:32].[C:26]1([S:23]([C:20]2[C:18]3=[N:19][C:14]([N:11]4[CH2:12][CH2:13][NH:8][CH2:9][CH2:10]4)=[CH:15][CH:16]=[C:17]3[NH:22][CH:21]=2)(=[O:25])=[O:24])[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

4

Reactant 2

HCID 5213051-Chloroethyl chloroformateHCID 58934070HCID 58934070, compound

Product 1

HCID 69060680HCID 69060680, compound

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

A stirred mixture of 5-(4-benzylpiperazin-1-yl)-3-(phenylsulfonyl)-1H-pyrrolo[3,2-b]pyridine (0.865 g, 2.00 mmol) and 1-chloroethylchloroformate (0.65 mL, 6.00 mmol) in 1,2-dichloroethane is heated at reflux temperature for 2.5 h under nitrogen, cooled and concentrated in vacuo, and reconcentrated from CH2Cl2 to a solid. This solid is heated with ethanol at reflux temperature under nitrogen for 2 h, cooled and concentrated in vacuo. The resultant residue is stirred in ethanol for 16 h and filtered. The filtercake is heated with methanol and two drops of concentrated hydrochloric acid for 30 h and concentrated in vacuo to a solid. This solid is chromatographed (silica gel, 5:95 concentrated ammonium hydroxide:ethanol as eluent) to afford the free amine of the title compound as a white solid. The free amine is dissolved in methanol, treated with 2.0 M aqueous hydrochloric acid (1.1 mL, 2.2 mmol) and concentrated to an off-white solid residue. This residue is recystallized from methanol to afford the title compound as an off-white solid, 165 mg (24% yield), mp 198-203° C. (foams), identified by NMR and mass spectral analyses.

Workup

  1. temperatureis heated
  2. temperatureat reflux temperature for 2.5 h under nitrogen
  3. temperaturecooled
  4. concentrationconcentrated in vacuo
  5. temperatureThis solid is heated with ethanol
  6. temperatureat reflux temperature under nitrogen for 2 h
  7. temperaturecooled
  8. concentrationconcentrated in vacuo
  9. filtrationfiltered
  10. temperatureThe filtercake is heated with methanol and two drops of concentrated hydrochloric acid for 30 h
  11. concentrationconcentrated in vacuo to a solid
  12. customThis solid is chromatographed (silica gel, 5:95 concentrated ammonium hydroxide:ethanol as eluent)

Sources & evidence

ORD record
ord-a937123f0ada48df80d821463fb4ee39
Source dataset
uspto-grants-2009_08
Patent number
US07576087B2

Reaction notes

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