Reaktion #676721

Reaktionsgleichung

N2

lithium acetylide

NaI

10-chloro-1,1-diethoxydecane

→

12,12-diethoxydodec-1-yne

Ausbeute 93.0%

Lösungsmittel

DMSO

Reaktionsbedingungen

Aufarbeitung

1. 1
   Temperaturwhile maintaining
2. 2
   Sonstigereaction temperature around 30° C.
3. 3
   WaschenThe addition funnel was rinsed with DMSO (15 ml, anhyrdrous, Su: Acros)
4. 4
   SonstigeThe solution was monitored by GC for compound 3 consumption (compound 3<2.0 Area % by GC)
5. 5
   workup.ADDITIONH2O (200 ml) were charged into the reaction mixture
6. 6
   Sonstigeto quench
7. 7
   Sonstigethe reaction
8. 8
   ExtraktionThe aqueous layer was extracted with heptane (2×200 ml)
9. 9
   FiltrationThe organic layer was filtered through a plug of Celite® 521 (15 g, Su: Sigma-Aldrich) one by one
10. 10
    Sonstigeafter phase separation
11. 11
    WaschenThe combined filtrate was washed with a solution of H2O (100 ml) and brine (50 ml)
12. 12
    SonstigeThe water in this organic solution was removed by azeotropic distillation under normal conditions by means
13. 13
    workup.ADDITIONof adding
14. 14
    Sonstigeremoving heptane (repeat if necessary until KF=˜0.2%)
15. 15
    EinengenThe resultant solution was concentrated under reduced pressure (pot temperature ˜35° C.)

Vorschrift

To a dark solution of lithium acetylide, ethylenediamine complex (13.8 g, 134.90 mMol, (90%) Su: Aldrich) and NaI (0.78 g, 5.19 mMol, (99+%), Su: Acros) in DMSO (100 ml anhydrous (99.7%) Su: Acros) was charged 10-chloro-1,1-diethoxydecane 3 (27.48 g, 103.77 mMol Su: from step B) while maintaining reaction temperature around 30° C., under a blanket of N2. The addition funnel was rinsed with DMSO (15 ml, anhyrdrous, Su: Acros). The solution was monitored by GC for compound 3 consumption (compound 3<2.0 Area % by GC). After 4 hr stirring at 30° C., H2O (200 ml) were charged into the reaction mixture to quench the reaction. The aqueous layer was extracted with heptane (2×200 ml). The organic layer was filtered through a plug of Celite® 521 (15 g, Su: Sigma-Aldrich) one by one after phase separation. The combined filtrate was washed with a solution of H2O (100 ml) and brine (50 ml). The water in this organic solution was removed by azeotropic distillation under normal conditions by means of adding and removing heptane (repeat if necessary until KF=˜0.2%). The resultant solution was concentrated under reduced pressure (pot temperature ˜35° C.) to give 24.6 g of 12,12-diethoxydodec-1-yne 4 as an amber liquid (93% yield over steps A thru C, after C). This material was used without further purification. GC: column SP, Rt: 12.2 for 10-chloro-1,1-diethoxydecane 3, and Rt: 11.1 min for 12,12-diethoxydodec-1-yne 4 (<5 Area %). 1H NMR (CDCl3, 400 MHz): δ 4.48 (t, J=5.60, 1H), 3.6 (m, J=7.07 Hz, 2H), 3.5 (m, J=7.07 Hz, 2H), 2.18 (dt, J=7.10, 2.80 Hz, 2H), 1.94 (t, J=2.60 Hz, 1H), 1.6 (m, 2H), 1.52 (qn, J=7.2 Hz, 2H), 1.4 (m, 2H), 1.29 (br s, 10H), 1.20 (t, J=7.00 Hz, 6H).

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