Hydrochloric Acid → HCID 53373399, compound

HRID 1846200Notes

Reaction equation

HRID 1846200 reaction equation
Br[C:2]1[C:3]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22])=[N:4][C:5]([N:10]([CH3:12])[CH3:11])=[N:6][C:7]=1[O:8][CH3:9].C(N)CN.[Li]CCCC.C[O:33]B(OC)OC.OO.Cl>C1COCC1.O>[CH2:13]([C:3]1[C:2]([OH:33])=[C:7]([O:8][CH3:9])[N:6]=[C:5]([N:10]([CH3:12])[CH3:11])[N:4]=1)[CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22]

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 3301EthylenediamineHCID 8470Trimethyl borateHCID 67328112HCID 67328112, compoundHCID 178418339Butyllithium

Product 1

HCID 53373399HCID 53373399, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-5 °C

Procedure

To a stirred solution at −5° C. containing 500 mg (1.34 mmol) of 5-bromo-4-decyl-6-methoxy-N,N-dimethylpyrimidin-2-amine in 10 mL of anhydrous THF were added 202 μL (1.34 mmol) of N,N,N,N-tretamethyl ethylenediamine followed by 2.09 mL (3.35 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 440 μL (4.02 mmol) of trimethoxy boron and the reaction mixture was stirred at 23° C. for 1 h. Then to reaction mixture were added 3.46 mL of 30% aq H2O2. The reaction mixture was then stirred for 30 min and poured into 100 mL of water. The mixture was neutralized with diluted aq. HCl and extracted with two 100-mL portions of ethyl acetate. The combined organic solution was washed with a 100-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 4:1 hexanes-ethyl acetate afforded the expected product as white solid: yield 111 mg (27%); mp: 59-60° C.; silica gel TLC Rf=0.60 (4:1 hexanes-ethyl acetate); 1H-NMR (methanol-d4) δ 0.87 (t, 3H, J=6.4 Hz), 1.33-1.24 (br m, 14H), 1.62 (quint, 2H, J=7.2 Hz), 2.58 (dd, 2H, J=7.6, 7.6 Hz), 3.09 (s, 6H) and 3.91 (s, 3H); 13C NMR (methanol-d4) δ 13.05, 22.32, 27.62, 29.05, 29.15, 29.17, 29.29, 29.31, 30.58, 31.67, 36.32, 36.32, 52.23, 126.96, 155.92, 155.94 and 159.48.

Workup

  1. stirringthe reaction mixture was stirred at 23° C. for 1 h
  2. customThen to reaction mixture
  3. stirringThe reaction mixture was then stirred for 30 min
  4. extractionextracted with two 100-mL portions of ethyl acetate
  5. washThe combined organic solution was washed with a 100-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 4:1 hexanes-ethyl acetate

Sources & evidence

ORD record
ord-c68c319c99b94ec08709e374fd42c1c4
Source dataset
uspto-grants-2015_02
Patent number
US08952025B2

Reaction notes

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