Hydrochloric Acid → HCID 67329355, compound

HRID 1846196Notes

Reaction equation

HRID 1846196 reaction equation
Br[C:2]1[C:3]([O:25][CH3:26])=[N:4][C:5]([N:22]([CH3:24])[CH3:23])=[N:6][C:7]=1[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][O:18][CH2:19][O:20][CH3:21].[Li]CCCC.C[O:33]B(OC)OC.OO.[OH-].[Na+].Cl>C1COCC1.O>[CH3:23][N:22]([CH3:24])[C:5]1[N:4]=[C:3]([O:25][CH3:26])[C:2]([OH:33])=[C:7]([CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][O:18][CH2:19][O:20][CH3:21])[N:6]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 8470Trimethyl borateHCID 14798Sodium HydroxideHCID 67328038HCID 67328038, compoundHCID 178418339Butyllithium

Product 1

HCID 67329355HCID 67329355, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-5 °C

Procedure

To a stirred solution at −5° C. containing 120 mg (0.25 mmol) of 5-bromo-4-methoxy-6-(10-(methoxymethoxy)decyl)-N,N-dimethylpyrimidin-2-amine in 3 mL of anhydrous THF were added 390 μL (0.62 mmol) of 1.6 M solution of n-BuLi in hexanes. The reaction mixture was stirred at −5° C. for 20 min. Then to the mixture were added 84 μL (0.75 mmol) of trimethoxy boron and the reaction mixture was stirred for 1 h. Then to reaction mixture were added 0.55 mL of 30% aq. H2O2 followed by 0.18 mL of 3N aq. NaOH. The reaction mixture was stirred for 30 min and poured into 50-mL of water. The mixture was neutralized with diluted aq. HCl and extracted with two 50-mL portions of ethyl acetate. The combined organic solution was washed with a 80-mL portion of brine, dried (MgSO4) and concentrated under diminished pressure. The residue was purified by chromatography on a silica gel column (10×3 cm). Elution with 2:1 hexanes-ethyl acetate afforded the expected product as colorless oil: yield 47 mg (51%); silica gel TLC Rf 0.50 (2:1 hexanes-ethyl acetate); 1H NMR (CDCl3) δ 1.29-1.21 (br m, 10H), 1.64-1.54 (m, 4H), 2.58 (br s, 2H), 3.07 (s, 6H), 3.33 (s, 3H), 3.48 (t, 2H, J=6.8 Hz), 3.92 (s, 3H) and 4.59 (s, 2H); 13C NMR (CDCl3) δ 26.14, 27.65, 29.29, 29.37, 29.42, 29.45, 29.52, 29.69, 31.19, 37.21, 37.21, 53.24, 55.03, 67.86, 96.32, 126.92, 154.98, 155.94 and 158.04; mass spectrum (APCI+), m/z 370.2700 (M+H) (C19H36N3O3 requires 370.2706).

Workup

  1. stirringthe reaction mixture was stirred for 1 h
  2. customThen to reaction mixture
  3. stirringThe reaction mixture was stirred for 30 min
  4. extractionextracted with two 50-mL portions of ethyl acetate
  5. washThe combined organic solution was washed with a 80-mL portion of brine
  6. dry with materialdried (MgSO4)
  7. concentrationconcentrated under diminished pressure
  8. customThe residue was purified by chromatography on a silica gel column (10×3 cm)
  9. washElution with 2:1 hexanes-ethyl acetate

Sources & evidence

ORD record
ord-7ac2eb4381ad4713ac8c2845c025b326
Source dataset
uspto-grants-2015_02
Patent number
US08952025B2

Reaction notes

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