Hydrochloric Acid → HCID 86668059, compound

HRID 474088Notes

Reaction equation

HRID 474088 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH2:9][N+:10]([O-:12])=[O:11])[C:5]([Cl:8])=[N:6][CH:7]=1.[CH2:13]=[O:14].C(N(CC)CC)C.[Na+].[Cl-].Cl.[O:25]1CCOC[CH2:26]1>>[Br:1][C:2]1[CH:3]=[C:4]([C:9]([N+:10]([O-:12])=[O:11])([CH2:13][OH:14])[CH2:26][OH:25])[C:5]([Cl:8])=[N:6][CH:7]=1

Participants

7

Reactant 6

HCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 5234Sodium ChlorideHCID 8471TriethylamineHCID 312751,4-DioxaneHCID 86668060HCID 86668060, compound

Product 1

HCID 86668059HCID 86668059, compound

Procedure

To a solution of 5-bromo-2-chloro-3-nitromethyl-pyridine (286 mg, 1.14 mmol) in dioxane (2.3 ml) was added 35% aq. formaldehyde (215 mg, 2.50 mmol), triethylamine (0.079 ml, 0.57 mmol) and the reaction mixture was stirred at room temperature for 2 h, to the mixture was added a mixture of saturated aq. NaCl and 12N HCl (0.05 ml, 0.6 mmol). Then the mixture was extracted with TBME the combined organic layers were washed with saturated aq. NaCl, dried with Na2SO4 and evaporated. The residue was purified by chromatography on silica gel (cyclohexane to cyclohexane/EtOAc 1:1) to provide the title compound as colorless solid. M.p. 162-163° C. HPLC: RtH4=0.69 min; ESIMS [M+H]+=311.0, 313.0; 1H NMR (600 MHz, DMSO-d6): 8.64 (d, 1H), 8.11 (d, 1H), 5.60 (t, 2H), 4.34 (dd, 2H), 4.19 (dd, 2H).

Workup

  1. additionwas added
  2. extractionThen the mixture was extracted with TBME the combined organic layers
  3. washwere washed with saturated aq. NaCl
  4. dry with materialdried with Na2SO4
  5. customevaporated
  6. customThe residue was purified by chromatography on silica gel (cyclohexane to cyclohexane/EtOAc 1:1)

Sources & evidence

ORD record
ord-58d463c1dc7942f4a2c4aa34638df3b8
Source dataset
uspto-grants-2014_01
Patent number
US08637508B2

Reaction notes

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