Hydrochloric Acid → HCID 53373129, compound

HRID 1846202Notes

Reaction equation

HRID 1846202 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][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])=[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:39]B(OC)OC.OO.Cl>C1COCC1.O>[CH3:11][N:10]([CH3:12])[C:5]1[N:4]=[C:3]([CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH3:28])[C:2]([OH:39])=[C:7]([O:8][CH3:9])[N:6]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 3301EthylenediamineHCID 8470Trimethyl borateHCID 67329292HCID 67329292, compoundHCID 178418339Butyllithium

Product 1

HCID 53373129HCID 53373129, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-5 °C

Procedure

To a stirred solution at −5° C. containing 500 mg (1.10 mmol) of 5-bromo-4-hexadecyl-6-methoxy-N,N-dimethylpyrimidin-2-amine in 10 mL of anhydrous THF were added 166 μL (1.10 mmol) of N,N,N,N-tretamethyl ethylenediamine followed by 1.72 mL (2.75 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 369 μL (3.30 mmol) of trimethoxy boron and the reaction mixture was stirred at 23° C. for 1 h. Then to reaction mixture were added 2.84 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 240 mg (55%); mp: 78-79° C.; silica gel TLC Rf=0.50 (4:1 hexanes-ethyl acetate); 1H-NMR (dmso-d6) δ 0.81 (t, 3H, J=6.0 Hz), 1.23-1.19 (br m, 26H), 1.52 (quint, 2H, J=6.8 Hz), 2.46 (dd, 2H, J=7.2, 7.2 Hz), 2.97 (s, 6H) and 3.82 (s, 3H); 13C NMR (dmso-d6) δ 14.38, 22.53, 27.65, 29.14, 29.27, 29.32, 29.38, 29.43, 29.46, 29.46, 29.46, 29.46, 29.46, 29.46, 31.20, 31.73, 37.27, 37.27, 53.13, 127.10, 155.54, 156.81 and 159.70.

Workup

  1. stirringthe reaction mixture was stirred at 23° C. for 1 h
  2. customThen to reaction mixture
  3. stirringwas 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-e4800c4f9dff488fa0e31b85066640a9
Source dataset
uspto-grants-2015_02
Patent number
US08952025B2

Reaction notes

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