Triethylamine → Ethyl phenyl-{4-(isopropoxy)-3-vinylphenyl}phosphinate

HRID 1960189Notes

Reaction equation

HRID 1960189 reaction equation
[C:1]1([PH:7](=[O:11])[O:8][CH2:9][CH3:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.Br[C:13]1[CH:18]=[CH:17][C:16]([O:19][CH:20]([CH3:22])[CH3:21])=[C:15]([CH:23]=[CH2:24])[CH:14]=1.C(N(CC)CC)C>C(#N)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2]>[C:1]1([P:7]([C:13]2[CH:18]=[CH:17][C:16]([O:19][CH:20]([CH3:21])[CH3:22])=[C:15]([CH:23]=[CH2:24])[CH:14]=2)(=[O:11])[O:8][CH2:9][CH3:10])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 3

HCID 8471TriethylamineHCID 125424254-Bromo-1-isopropoxy-2-vinylbenzeneHCID 178476779HCID 178476779, compound

Product 1

HCID 66650560Ethyl phenyl-{4-(isopropoxy)-3-vinylphenyl}phosphinateYield 87%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 635956Ferrocene-1,1'-bis-(diphenylphosphine)CatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
68 °C

Procedure

To a degassed mixture of ethyl phenylphosphinate (1.87 g, 11.0 mmol) and 4-bromo-1-isopropoxy-2-vinylbenzene (2.43 g, 10.0 mmol), which was commercially available, in acetonitrile (66 mL) were added triethylamine (3.1 mL, 22.0 mmol), palladium acetate (112 mg, 0.5 mmol), and 1,1′-bis(diphenylphosphino)ferrocene (277 mg, 0.5 mmol). The mixture was further degassed and heated at 68° C. for 24 hrs. The volatiles were removed in vacuo, and the crude was purified by column chromatography using 50 to 80% ethyl acetate in petroleum ether to afford compound BA4 (3.74 g) in 87% yield. 1H NMR (CDCl3, 400 MHz): δ (ppm) 1.36 (d, J=5.7 Hz, 6H), 1.37 (t, J=6.9 Hz, 3H), 4.15-4.05 (m, 2H), 4.62 (sept., J=6.0 Hz, 1H), 5.28 (dd, J=11.2 and 1.4 Hz, 1H), 5.78 (dd, J=17.7 and 1.4 Hz, 1H), 6.91 (dd, J=8.45 and 3.0 Hz, 1H), 6.99 (dd, J=17.9 and 11.4 Hz, 1H), 7.41-7.47 (m, 2H), 7.47-7.55 (m, 1H), 7.63 (ddd, J=11.7, 8.5 and 2.0 Hz, 1H), 7.79 (dd, J=12.3 and 1.4 Hz, 1H), 7.81 (dt, J=12.3 and 1.4 Hz, 1H), 7.90 (dd, J=12.4 and 2.0 Hz, 1H); 31P NMR (CDCl3, 161.8 MHz): δ (ppm) 32.61.

Workup

  1. customThe mixture was further degassed
  2. customThe volatiles were removed in vacuo
  3. customthe crude was purified by column chromatography
  4. customto afford compound BA4 (3.74 g) in 87% yield

Sources & evidence

ORD record
ord-8af9eadaed814cfc84762f8f13e69de7
Source dataset
uspto-grants-2013_04
Patent number
US08410313B2

Reaction notes

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