반응 #3764

반응 방정식

4-heptanone

ethyl cyanoacetate

Acetic

→

Ethyl α-cyano-α-(4-heptylidene)acetate

용매

cyclohexane

ethyl acetate

반응 조건

후처리

1. 1
   workup.ADDITIONwere added
2. 2
   온도heated
3. 3
   온도to reflux with a Dean-Stark trap in place overnight under N2
4. 4
   온도The reaction was cooled to ambient,
5. 5
   세척washed with H2O (2×50 mL) and brine (25 mL)
6. 6
   건조The organic extracts were dried (Na2SO4
7. 7
   여과filtered
8. 8
   농축concentrated under vacuum
9. 9
   기타to give an oil that
10. 10
    workup.DISTILLATIONwas distilled (bp. 135°-137° C., 20 mmHg)

실험 절차

In a 100 mL round-bottom flask was dissolved 4-heptanone (11.4 g, 0.10 mmole) and ethyl cyanoacetate (11.30 g, 0.100 mole) in cyclohexane (25 mL). Acetic add (1.0 mL) and NH4OAc (2.0 g) were added. The solution was magnetically stirred and heated to reflux with a Dean-Stark trap in place overnight under N2. The reaction was cooled to ambient, diluted with ethyl acetate (100 mL) washed with H2O (2×50 mL) and brine (25 mL). The organic extracts were dried (Na2SO4, filtered and concentrated under vacuum to give an oil that was distilled (bp. 135°-137° C., 20 mmHg) to give Ethyl α-cyano-α-(4-heptylidene)acetate (16.65 g, 0.080 mole, 80%). IR (neat film) 2950, 2910, 2860, 2200, 1725, 1570, 1235, 1085 cm-1 ; 1H NMR (400 MHz, CDCl3 δ 4.15 (q, J=9 Hz, 2H), 2.60 (t, J=10 Hz, 2H), 2.38 (t, J=10 Hz, 2H), 1.25 (t, J=9 Hz, 2H), 1.40 (sextet, J=9 Hz, 2H), 1.25 (t, J=9 Hz, 3H), 0.88 (m, 6H); 13C NMR (100 MHz, CDCl3) δ 181.2, 161.5, 115.5, 104.6, 61.4, 40.2, 35.2, 21.9, 21.4, 14.1, 13.8 (one carbon not observed due to overlap); MS (CI) m/e 211 (14.5), 210 (100), 209 (3.59), 182 (3.5), 164 (2.8); HRMS (CI) calcd for C12H20NO2 (M+H) m/e 210.1484, found 210.1491.

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