Hydrochloric Acid → HCID 86668061, compound

HRID 538350Notes

Reaction equation

HRID 538350 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([C:9]([N+:14]([O-])=O)([CH2:12][OH:13])[CH2:10][OH:11])[C:5]([Cl:8])=[N:6][CH:7]=1.N1C=CC=CC=1.[Cl:23][CH2:24][C:25](Cl)=[O:26].Cl.C([O-])([O-])=O.[K+].[K+]>C(Cl)Cl.CC(OC)(C)C>[Br:1][C:2]1[CH:3]=[C:4]([C:9]([NH:14][C:25](=[O:26])[CH2:24][Cl:23])([CH2:12][OH:13])[CH2:10][OH:11])[C:5]([Cl:8])=[N:6][CH:7]=1

Participants

8

Reactant 5

HCID 313Hydrochloric Acid2×HCID 1049PyridineHCID 6577Chloroacetyl chlorideHCID 11430Potassium CarbonateHCID 86668059HCID 86668059, compound

Product 1

HCID 86668061HCID 86668061, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent3×HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
-30 °C

Procedure

To a suspension of 2-(5-bromo-2-chloro-pyridin-3-yl)-2-nitropropane-1,3-diol (904 mg, 3.21 mmol) in DCM (64 ml) was added pyridine (2.6 ml, 32.1 mmol), after cooling to −30° C. a solution of chloro-acetylchloride (1.022 ml, 12.84 mmol) in DCM (32 ml) was added within 10 min., the reaction mixture was stirred at −30° C. for 1.5 h. At −30° C. 1M HCl and DCM was added, the layers were separated, the aq. phase extracted with DCM and the combined organic layers washed with halfsaturated aq. NaHCO3 and halfsaturated aq. NaCl, dried with Na2SO4 and evaporated. The obtained per-acetylated product was dissolved in methanol (19.3 ml) and K2CO3 powder (222 mg, 1.6 mmol) added, the mixture was stirred at room temperature for 30 min. After addition of 1M HCl and TBME the layers were separated, the aq. layer was extracted with TBME, the combined organic layers were washed with halfsaturated aq. NaCl, dried with Na2SO4 and evaporated. The residue was purified by chromatography on silica gel (cyclohexane/EtOAc 1:0 to cyclohexane/EtOAc 0:1) to provide the title compound as colorless solid.

Workup

  1. additionwas added within 10 min.
  2. customAt −30° C
  3. customthe layers were separated
  4. extractionthe aq. phase extracted with DCM
  5. washthe combined organic layers washed with halfsaturated aq. NaHCO3 and halfsaturated aq. NaCl
  6. dry with materialdried with Na2SO4
  7. customevaporated
  8. dissolutionThe obtained per-acetylated product was dissolved in methanol (19.3 ml)
  9. stirringthe mixture was stirred at room temperature for 30 min
  10. customwere separated
  11. extractionthe aq. layer was extracted with TBME
  12. washthe combined organic layers were washed with halfsaturated aq. NaCl
  13. dry with materialdried with Na2SO4
  14. customevaporated
  15. customThe residue was purified by chromatography on silica gel (cyclohexane/EtOAc 1:0 to cyclohexane/EtOAc 0:1)

Sources & evidence

ORD record
ord-58a62ec867f64993be0e3bbbd8670241
Source dataset
uspto-grants-2014_10
Patent number
US08865712B2

Reaction notes

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