Thionyl Chloride → HCID 59418741, compound

HRID 1896587Notes

Reaction equation

HRID 1896587 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

Thionyichloride (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-833ec5cfcf724bd2963d0c359f112f67
Source dataset
uspto-grants-2013_08
Patent number
US08518970B2

Reaction notes

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