1,3-Propanedithiol → Diethyl vinylphosphonate

HRID 341712

Reaktionsgleichung

Reaktionsgleichung von HRID 341712
[H-].[Na+].SCCCS.Br[CH2:9][CH2:10][P:11]([O:16][CH2:17][CH3:18])([O:13][CH2:14][CH3:15])=[O:12]>CCCCCC>[CH:10]([P:11](=[O:12])([O:16][CH2:17][CH3:18])[O:13][CH2:14][CH3:15])=[CH2:9]

Komponenten

5

Edukt 3

HCID 80131,3-PropanedithiolHCID 24758Sodium hydrideHCID 79218Diethyl (2-bromoethyl)phosphonate

Produkt 1

HCID 69629Diethyl vinylphosphonateAusbeute 90 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

A sample of 60% NaH in mineral oil (95 mmol) was placed in a 2-neck round bottom flask and charged with dry hexane (20 mL). This solution was allowed to stir for ten minutes, after which the hexane-mineral oil layer was completely removed. The flask was then charged with dry tetrahydrofuran (100 mL), followed by dropwise addition of HS(CH2)3SH (46 mmol) with constant stirring. The resulting solution was cooled at 0° C. and BrCH2CH2P(O)(OC2H5)2 (95 mmol) was added dropwise with constant stirring over a period of 30 minutes. Excess NaH was quenched by addition of 50 mL of deionized water. The solution was extracted from ethyl acetate (3×50 mL) and washed with a saturated sodium chloride solution. The organic layer was dried over anhydrous sodium sulfate. Upon filtering, the solvent was removed in vacuo to afford compound 5 in 90% yield along with a trace amount of diethyl vinylphosphonate. The compounds were separated on a silica gel column (20 cm; 60 mesh) using 90:10 ethyl acetate to hexane solvent mixture. Removal of the solvent in vacuo, afforded compound 5 as a viscous, yellow-green oil with an overall yield of 88%. High resolution FAB/MS Anal. Calcd. for C15H34O6P2S2 : 436.1272; Found: [M+H+ ], m/z=437.1350. 1H NMR (CDCl3): δ 1.34 (t, 3JHH =9.0 Hz, 12H, OCH2CH3), 1.87 (qn, 2H, CH2CH2CH2), 2.03 (m, 4H, PCH2CH2), 2.65 (t, 3JHH =9.0 Hz, 4H, CHCH2CH2), 2.74 (m, 4H, PCH2CH2), 4.11 (m, 8H, OCH2CH3). 13C NMR (CHCl3): δ 16.3 (d, 3JPC =4.5 Hz, OCH2CH3), 24.8 (d, 2JPC =3.0 Hz, PCH2CH2), 26.6 (d, 1JPC =136.6 Hz, PCH2CH2), 28.5 (s, CH2CH2CH2), 30.5 (s, CH2CH2CH2), 61.6 (d, 2JPC= 6.0 Hz OCH2CH3). 31P NMR (CDCl3): δ 29.1 (s).

Aufarbeitung

  1. customafter which the hexane-mineral oil layer was completely removed
  2. additionThe flask was then charged with dry tetrahydrofuran (100 mL)
  3. stirringwith constant stirring over a period of 30 minutes
  4. customExcess NaH was quenched by addition of 50 mL of deionized water
  5. extractionThe solution was extracted from ethyl acetate (3×50 mL)
  6. washwashed with a saturated sodium chloride solution
  7. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  8. filtrationUpon filtering
  9. customthe solvent was removed in vacuo

Quellen und Nachweise

ORD-Eintrag
ord-7d5e6016330d453db7e38c0ab760686b
Quelldatensatz
uspto-grants-1999_01
Patentnummer
US05855867

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