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

HRID 265241Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 265241
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]

Komponenten

7

Edukt 4

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

Produkt 1

HCID 67708256Ethyl E-2-phosphono-3-[2-(1-tridecynyl)phenyl]propenoateAusbeute 47,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 180AcetoneLösungsmittelHCID 6344DichloromethaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

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)+.

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-07d6f62192e34a4eb18562720eca2118
Quelldatensatz
uspto-grants-1997_07
Patentnummer
US05648349

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