Thionyl Chloride → HCID 59418741, compound

HRID 2178237Notes

Reaction equation

HRID 2178237 reaction equation
S(Cl)([Cl:3])=O.[NH2:5][C:6]1[CH:11]=[C:10]([Br:12])[CH:9]=[CH:8][C:7]=1[N:13]([CH3:17])[CH2:14][CH2:15]O>C(Cl)Cl.CN(C=O)C>[Br:12][C:10]1[CH:11]=[C:6]([NH2:5])[C:7]([N:13]([CH2:14][CH2:15][Cl:3])[CH3:17])=[CH:8][CH:9]=1

Participants

5

Reactant 2

HCID 24386Thionyl ChlorideHCID 43345909HCID 43345909, compound

Product 1

HCID 59418741HCID 59418741, compoundYield 41.2%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent

Procedure

Thionylchloride (0.78 g, 6.74 mmol) was added dropwise to a solution of 2-((2-amino-4-bromophenyl)(methyl)amino)ethanol (25C) (1.376 g, 5.62 mmol) in DCM (50 mL) and DMF (10 drops) at 0° C. The mixture was allowed to warm up to rt and stirred for 1 hour. Then, the mixture was heated to 35° C. for 2.5 hours, concentrated, diluted with 1N NaOH, and extracted with DCM. The organic phases were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE:EtOAc 100:0-85:15, to provide 0.611 g (41%) of the desired product 4-bromo-N1-(2-chloroethyl)-N1-methylbenzene-1,2-diamine (25D): 1H NMR (300 MHz, CDCl3) δ 6.88-6.79 (3H, m), 4.20 (2H, bs), 3.56 (2H, t), 3.17 (2H, t), 2.67 (3H, s).

Workup

  1. temperatureThen, the mixture was heated to 35° C. for 2.5 hours
  2. concentrationconcentrated
  3. additiondiluted with 1N NaOH
  4. extractionextracted with DCM
  5. washThe organic phases were washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe crude material was purified by flash column chromatography on silica gel eluting with a gradient of PE

Sources & evidence

ORD record
ord-9dd4d0efa6c54b7cb0afa5781fcb0a7a
Source dataset
uspto-grants-2015_06
Patent number
US09067928B2

Reaction notes

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