Hydrochloric Acid → 1-(3-Bromo-5-chloro-2-methoxy-4-methylphenyl)ethanamine

HRID 510902Notes

Reaction equation

HRID 510902 reaction equation
[Br:1][C:2]1[C:3]([O:20][CH3:21])=[C:4]([CH:10]([NH:12]C(=O)OC(C)(C)C)[CH3:11])[CH:5]=[C:6]([Cl:9])[C:7]=1[CH3:8].Cl.O1CCOCC1>C(=O)(O)[O-].[Na+]>[Br:1][C:2]1[C:3]([O:20][CH3:21])=[C:4]([CH:10]([NH2:12])[CH3:11])[CH:5]=[C:6]([Cl:9])[C:7]=1[CH3:8]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 312751,4-DioxaneHCID 88543336Tert-butyl[1-(3-bromo-5-chloro-2-methoxy-4-methylphenyl)ethyl]carbamate

Product 1

HCID 866668191-(3-Bromo-5-chloro-2-methoxy-4-methylphenyl)ethanamine

Reagents, catalysts & solvents 1

HCID 516892Sodium BicarbonateSolvent

Procedure

A mixture of tert-butyl [1-(3-bromo-5-chloro-2-methoxy-4-methylphenyl)ethyl]carbamate (0.84 g, 2.2 mmol) (second peak from chiral separation) was treated with 4.0 M hydrogen chloride in dioxane (3.0 mL, 12 mmol) at room temperature for 2 hours. The mixture was diluted with saturated sodium bicarbonate solution and extracted with dichloromethane. The combined organic layers were dried over MgSO4, filtered and concentrated to give 1-(3-bromo-5-chloro-2-methoxy-4-methylphenyl)ethanamine, which was combined with 6-bromo-9-(tetrahydro-2H-pyran-2-yl)-9H-purine (0.82 g, 2.9 mmol, from Example 108, Step 1) and N,N-diisopropylethylamine (1.2 mL, 6.6 mmol) in ethanol (6 mL) and heated at 100° C. overnight. The reaction mixture was concentrated and purified on silica gel (eluting with 0-65% ethyl acetate in hexanes) to afford the desired product. LCMS calculated for C20H24BrClN5O2 (M+H)+: m/z=480.1, 482.1. found: 480.0, 482.0.

Workup

  1. extractionextracted with dichloromethane
  2. dry with materialThe combined organic layers were dried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-670bfbaba0944346a87b7f11f1399183
Source dataset
uspto-grants-2015_08
Patent number
US09096600B2

Reaction notes

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