Triethylamine → 6-(Ethoxy(diethylphosphonomethyl)phosphinoyl)-3,4-dihydro-4,4-dimethylchromen-2-one

HRID 39275Notes

Reaction equation

HRID 39275 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][C:7](=[O:12])[CH2:6][C:5]2([CH3:14])[CH3:13].[CH2:15]([O:17][P:18]([CH2:23][PH:24]([O:26][CH2:27][CH3:28])=[O:25])(=[O:22])[O:19][CH2:20][CH3:21])[CH3:16].C(N(CC)CC)C>C(#N)C.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH2:27]([O:26][P:24]([CH2:23][P:18]([O:17][CH2:15][CH3:16])([O:19][CH2:20][CH3:21])=[O:22])([C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[O:8][C:7](=[O:12])[CH2:6][C:5]2([CH3:14])[CH3:13])=[O:25])[CH3:28]

Participants

6

Reactant 3

HCID 8471TriethylamineHCID 225689232H-1-Benzopyran-2-one, 6-bromo-3,4-dihydro-4,4-dimethyl-HCID 178476825HCID 178476825, compound

Product 1

HCID 251393606-(Ethoxy(diethylphosphonomethyl)phosphinoyl)-3,4-dihydro-4,4-dimethylchromen-2-oneYield 73.9%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 6342AcetonitrileSolvent2×

Conditions

Temperature
100 °C

Procedure

A mixture of 6-bromo-4,4-dimethylchroman-2-one (3.5 g, 9.7 mmol), diethyl(ethoxyphosphinyl)methylphosphonate (1.7 g, 9.7 mmol), triethylamine (4.1 mL, 29 mmol) and Pd(PPh3)4 (0.56 g, 0.48 mmol) in acetonitrile (20 mL) was heated to 100° C. for 18 hr. The reaction mixture was cooled and diluted with acetonitrile (50 mL) followed by washing with aqueous HCl (10%), water and saturated aqueous NaCl. The organic phase was dried over Na2SO4, filtered and concentrated. The crude product was purified by silica gel chromatography (0-10% methanol in CH2Cl2) on a Biotage™ flash chromatography system, resulting in 120 as pale yellow oil (3.0 g, 73%): 1H NMR (400 MHz, CDCl3) δ 1.21 (t, J=7.2, 3H), 1.30-1.37 (m, 6H), 1.40 (s, 6H), 2.61 (dd, J=1.7, 17.2, 20.7, 2H), 2.66 (s, 2H), 3.95-4.08 (m, 2H), 4.11-4.21 (m, 4H), 7.16 (dd, J=3.1, 8.3, 2H), 7.73 (dd, J=3.1, 8.3, 2H): 31P (162 MHz, CDCl3) δ 20.07 (d, J=7.7, 1 P), 33.74 (d, J=7.7, 1 P).

Workup

  1. temperatureThe reaction mixture was cooled
  2. washby washing with aqueous HCl (10%), water and saturated aqueous NaCl
  3. dry with materialThe organic phase was dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe crude product was purified by silica gel chromatography (0-10% methanol in CH2Cl2) on a Biotage™ flash chromatography system

Sources & evidence

ORD record
ord-4927a3cecd9546f28d3bb8ba398f7ef4
Source dataset
uspto-grants-2013_09
Patent number
US08524691B2

Reaction notes

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