Methyl Acrylate → HCID 86677849, compound

HRID 1499932Notes

Reaction equation

HRID 1499932 reaction equation
[Cl:1][C:2]1[C:3]([CH3:25])=[C:4](I)[C:5]([O:21][CH2:22][CH3:23])=[C:6]([CH:8]([N:10]2[C:14]3=[N:15][CH:16]=[N:17][C:18]([NH2:19])=[C:13]3[C:12]([CH3:20])=[N:11]2)[CH3:9])[CH:7]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[C:45]([O:49][CH3:50])(=[O:48])[CH:46]=[CH2:47].C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:19][C:18]1[N:17]=[CH:16][N:15]=[C:14]2[N:10]([CH:8]([C:6]3[C:5]([O:21][CH2:22][CH3:23])=[C:4](/[CH:47]=[CH:46]/[C:45]([O:49][CH3:50])=[O:48])[C:3]([CH3:25])=[C:2]([Cl:1])[CH:7]=3)[CH3:9])[N:11]=[C:12]([CH3:20])[C:13]=12

Participants

7

Reactant 4

HCID 7294Methyl AcrylateHCID 8471TriethylamineHCID 11776TriphenylphosphineHCID 86677850HCID 86677850, compound

Product 1

HCID 86677849HCID 86677849, compoundYield 72%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

A suspension of 1-[1-(5-chloro-2-ethoxy-3-iodo-4-methylphenyl)ethyl]-3-methyl-1H-pyrazolo[3,4-d]pyrimidin-4-amine (peak 1 single isomer from step 2) (0.61 g, 1.3 mmol) in acetonitrile (7.4 mL) in a sealed tube was degassed with nitrogen and treated with triphenylphosphine (0.048 g, 0.18 mmol), methyl acrylate (0.41 mL, 4.5 mmol), and palladium acetate (0.029 g, 0.13 mmol) followed by triethylamine (0.54 mL, 3.9 mmol) and heated at 100° C. for 16 h. The reaction mixture was cooled to room temperature, filtered, and the solids washed with acetonitrile. The filtrate was concentrated to a residue. The crude material was purified by flash column chromatography using ethyl acetate (containing 3% methanol) in hexanes (0%-100%) to give the desired product (0.40 g, 72%). LCMS for C21H25ClN5O3 (M+H)+: m/z=430.2; Found: 430.2.

Workup

  1. customwas degassed with nitrogen
  2. temperatureThe reaction mixture was cooled to room temperature
  3. filtrationfiltered
  4. washthe solids washed with acetonitrile
  5. concentrationThe filtrate was concentrated to a residue
  6. customThe crude material was purified by flash column chromatography

Sources & evidence

ORD record
ord-41ab00c1516242c08ffc3d32c03a2d7c
Source dataset
uspto-grants-2015_12
Patent number
US09199982B2

Reaction notes

Loading…