(3-Aminopropyl)triethoxysilane → HCID 178476784, compound

HRID 448837Notes

Reaction equation

HRID 448837 reaction equation
I[C:2]1[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=[C:4]([C:12]([F:15])([F:14])[F:13])[CH:3]=1.[PH2:16]([O-:18])=[O:17].[NH3+][C:20]1C=CC=C[CH:21]=1.NCCC[Si](OCC)(OCC)OCC.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(#N)C.C(OCC)(=O)C.Cl.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[F:13][C:12]([F:15])([F:14])[C:4]1[CH:3]=[C:2]([PH:16](=[O:18])[O:17][CH2:20][CH3:21])[CH:7]=[C:6]([C:8]([F:11])([F:10])[F:9])[CH:5]=1

Participants

9

Reactant 4

HCID 13521(3-Aminopropyl)triethoxysilaneHCID 812191,3-Bis(diphenylphosphino)propaneHCID 6309701-Iodo-3,5-bis(trifluoromethyl)benzeneHCID 178527020HCID 178527020, compound

Product 1

HCID 178476784HCID 178476784, compoundYield 52%

Reagents, catalysts & solvents 4

HCID 167845palladium(II) acetateCatalystHCID 313Hydrochloric AcidSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a degassed solution of 1-iodo-3,5-bistrifluoromethylbenzene (10.0 g, 29.4 mmol), anilinium hypophosphite (5.62 g, 35.3 mmol) and 3-aminopropyl triethoxysilane (7.81 g, 35.3 mmol) in anhydrous acetonitrile (200 mL) were added palladium acetate (132 mg, 0.588 mmol, 2 mol %) and 1,3-bis(diphenylphosphino)propane (267 mg, 0.647 mol, 2.2 mol %). The mixture was refluxed overnight. After cooling down to room temperature, the reaction mixture was diluted with ethyl acetate and hydrochloric acid (1M), and then partitioned. The aqueous layer was further extracted with ethyl acetate. The combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine, and dried over sodium sulfate. The volatiles were removed in vacuo, and the residue was purified by column chromatography using 30 to 70% ethyl acetate in petroleum ether to afford compound AZ3 (4.65 g) as a cloudy oil in 52% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.45 (t, J=7.1 Hz, 3H), 4.18-4.35 (m, 2H), 7.69 (d, J=579.6 Hz, 1H), 8.10 (s, 1H), 8.23 (s, 1H), 8.27 (s, 1H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 19.59 (J=580.6 Hz).

Workup

  1. temperatureThe mixture was refluxed overnight
  2. custompartitioned
  3. extractionThe aqueous layer was further extracted with ethyl acetate
  4. washThe combined extracts were washed sequentially with aqueous sodium hydrogen carbonate and brine
  5. dry with materialdried over sodium sulfate
  6. customThe volatiles were removed in vacuo
  7. customthe residue was purified by column chromatography
  8. customto afford compound AZ3 (4.65 g) as a cloudy oil in 52% yield

Sources & evidence

ORD record
ord-62fa05aefde7445692d2c000ebf94519
Source dataset
uspto-grants-2013_07
Patent number
US08481748B2

Reaction notes

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