Water → Ethyl E-2-phosphono-3-[2-(1-tridecynyl)phenyl]propenoate

HRID 265241Notes

Reaction equation

HRID 265241 reaction equation
C([O:3][P:4]([O:32]CC)(/[C:6](=[CH:12]/[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:19]#[C:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])/[C:7]([O:9][CH2:10][CH3:11])=[O:8])=[O:5])C.Br[Si](C)(C)C.CC(C)=O.CCCCCCC.O>C(Cl)Cl.CC(C)=O>[P:4](/[C:6](=[CH:12]/[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][C:14]=1[C:19]#[C:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH3:31])/[C:7]([O:9][CH2:10][CH3:11])=[O:8])([OH:32])([OH:5])=[O:3]

Participants

7

Reactant 4

HCID 962Water2×HCID 76113BromotrimethylsilaneHCID 15284941Ethyl 2-(diethoxyphosphinyl)-3-[2-(1-tridecynyl)phenyl]-2-E-propenoateHCID 21879760Acetone heptane

Product 1

HCID 67708256Ethyl E-2-phosphono-3-[2-(1-tridecynyl)phenyl]propenoateYield 47.6%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

Ethyl 2-(diethoxyphosphinyl)-3-[2-(1-tridecynyl)phenyl]-2-E-propenoate (0.50 g, 1.02 mmol) prepared according to Example 5 was dissolved in dry CH2Cl2 (3 ml) and CD2Cl2 (2 ml, dried over activated neutral alumina) and cooled to 0° C. Bromotrimethylsilane (0.31 ml, 2.35 mmol) was added over a two to three minute period. The progress of the reaction was monitored by 31 p NMR, to follow disappearance of the starting material. After about 5 hours, the solvent was removed under reduced pressure. Acetone-heptane (5.5 ml, 10:1) containing 0.045 ml (2.5 mmol) water was added and the reaction was stirred for 1.5 hours. At the end of this time the solvent was stripped. Since NMR indicated incomplete reaction, acetone (5 ml) containing water (0.05 ml, 2.8 mmol) was added and stirring was continued for two hours. After stripping the solvent, the reaction was still incomplete. It required 2.5 more hours under these conditions to complete the reaction. The solvent was stripped off and the residue was chromatographed on silica eluting with 10% chloroform and 20% methanol in heptane. Fractions containing product were recrystallized from heptane yielding a white solid, 0.211 g, 0.486 mmol, 47.6% yield; mp 68°-69° C.; 1H NMR (CDCl3) ∂0.86 (m, 3H), 1.09 to 1.63 (several m, 21H), 2.40 (t, J=7.1 Hz, 2H), 4.19 (q, J=7.1 Hz, 2H), 7.17 to 7.44 (several m, 4H), 8.15 (d, J=24.7 Hz, 1H), 8.81 (br s, 2.7H); FAB mass spectrum m/z 434 (M+H)+.

Workup

  1. customthe solvent was removed under reduced pressure
  2. additionwas added
  3. additionwas added
  4. stirringstirring
  5. waitwas continued for two hours
  6. customthe reaction
  7. customthe residue was chromatographed on silica eluting with 10% chloroform and 20% methanol in heptane
  8. additionFractions containing product
  9. customwere recrystallized from heptane yielding a white solid, 0.211 g, 0.486 mmol, 47.6% yield

Sources & evidence

ORD record
ord-07d6f62192e34a4eb18562720eca2118
Source dataset
uspto-grants-1997_07
Patent number
US05648349

Reaction notes

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