Methanol → HCID 19873366, compound

HRID 466366Notes

Reaction equation

HRID 466366 reaction equation
[CH2:1]([N:3]([CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH2:4][CH:5]([C:7]1[CH:12]=[CH:11][C:10]([NH:13][S:14]([CH3:17])(=[O:16])=[O:15])=[CH:9][CH:8]=1)[OH:6])[CH3:2].[CH2:25]([Br:27])[CH3:26].CO>C(#N)C>[Br-:27].[CH2:1]([N+:3]([CH2:25][CH3:26])([CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH3:24])[CH2:4][CH:5]([OH:6])[C:7]1[CH:12]=[CH:11][C:10]([NH:13][S:14]([CH3:17])(=[O:15])=[O:16])=[CH:9][CH:8]=1)[CH3:2]

Participants

5

Reactant 3

HCID 887MethanolHCID 6332Ethyl Bromide2×HCID 14891483HCID 14891483, compound

Product 1

HCID 19873366HCID 19873366, compound

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

A stirred solution of N-[4-[2-(ethylheptylamino)-1-hydroxyethyl]phenyl]methanesulfonamide of Example 5 (1.5 g, 0.0042 mol) in acetonitrile (15 ml) is treated with ethyl bromide (6.12 ml, 0.082 mol) and refluxed under N2 for 4 days. Additional ethyl bromide is added and reflux is continued for 3 days. The reaction is still incomplete by TLC on silica gel with 5% MeOH-1% NH4OH--CH2Cl2. The mixture is concentrated and mixed with a solution of NaHCO3 (200 mg) in water and Et2O. The aqueous layer is extracted with Et2O and the Et2O extracts are washed with water. The combined water solution is made alkaline with 1N potassium hydroxide, saturated with potassium bromide and extracted with CH2Cl2. The CH2Cl2 extracts are washed with saturated potassium bromide. The combined aqueous layer is acidified with hydrogen bromide and extracted with CH2Cl2. These extracts are washed with saturated potassium bromide, dried (Na2SO4) and concentrated. This material is pure by HPLC on an RP-18 Spheri-10 column using a gradient of 50% H2O to 35% H2O--CH3CN with both solvents containing 0.2% TFA to yield N,N-diethyl-N-heptyl-β-hydroxy-4-[(methylsulfonyl)amino]benzeneethanaminium bromide.

Workup

  1. temperaturerefluxed under N2 for 4 days
  2. temperaturereflux
  3. concentrationThe mixture is concentrated
  4. additionmixed with a solution of NaHCO3 (200 mg) in water and Et2O
  5. extractionThe aqueous layer is extracted with Et2O
  6. washthe Et2O extracts are washed with water
  7. extractionsaturated with potassium bromide and extracted with CH2Cl2
  8. washThe CH2Cl2 extracts are washed with saturated potassium bromide
  9. extractionextracted with CH2Cl2
  10. washThese extracts are washed with saturated potassium bromide
  11. dry with materialdried (Na2SO4)
  12. concentrationconcentrated
  13. additioncontaining 0.2% TFA

Sources & evidence

ORD record
ord-fb82bb3ae598408db79e4029d5f90fc3
Source dataset
uspto-grants-1992_10
Patent number
US05155268

Reaction notes

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