Synthesis of 12-alkoxycarbonylmethylene-1,15-pentadecanolides
Synthesis of 12-alkoxycarbonylmethylene-1,15-pentadecanolides
摘要
Six novel 12-alkoxycarbonylmethylene-1,15-pentadecanolides (3) were synthesized from 2-nitrocyclo-dodecanone by the Michael addition with acrolein followed by ring enlargement, Nef reaction and Wittig-Homer reaction. Their structures were confirmed bv 1H NMR, IR and elemental analysis. The preliminary bioassay showed that they have some fungicidal activity.
Six novel 12-alkoxycarbonylmethylene-1,15-pentadecanolides (3) were synthesized from 2-nitrocyclo-dodecanone by the Michael addition with acrolein followed by ring enlargement, Nef reaction and Wittig-Homer reaction. Their structures were confirmed bv 1H NMR, IR and elemental analysis. The preliminary bioassay showed that they have some fungicidal activity.
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4[4]A suspension of 4 (4.5 mmol) and KOBu' (4.5 mmol,0.51 g) in anhydrous THF (50 mL) was heated at reflux for 1 h.The mixture was allowed to cool to room temperature before a solution of 2 (3 mmol,0.76 g) in dry THF (10 mL) was injected.The reaction mixture was heated for another 10 h,then cooled to room temperature and poured into Et2O/H2O (1:1,150 mL),the organic layer was separated and the aqueous phase was extracted with Et2O (50 mL×2).The combined extracts were washed with brine,dried with Na2SO4 and concentrated under reduced pressure.Purification by silica-gel column chromatography afforded 3 as colourless oil.3a:Yield:64%; 1HNMR (300 MHz,CDCl3,δppm):1.25-1.36 (m,13H),1.47-1.52 (m,2H),1.61-1.68 (m,2H),1.79-1.84 (m,2H),2.11-2.16 (m,1H),2.25-2.28 (m,1H),2.35 (t,2H,J= 10.5 Hz),2.59-2.62 (m,1H),2.68-2.74 (m,1H),3.68 (s,3H),4.13-4.21 (m,2H),5.65 (s),5.70 (s); IR,v:1720,1700,1640; anal.calcd.for C19H32O4:C 69.64,H 9.74;found:C 69.42,H 9.61.3b:Yield:73%; 1H NMR (300 MHz,CDCl3,δppm):1.25-1.36 (m,15H),1.47-1.52 (m,2H),1.64-1.68 (m,2H),1.79-1.85 (m,2H),2.10-2.15 (m,1H),2.24-2.31 (m,1H),2.35 (t,2H,J = 10.5 Hz,),2.59-2.61 (m,1H),2.68-2.73 (m,1H),4.10-4.20 (m,4H),5.65 (s),5.69 (s); IR,v:1720,1700,1640; anal.calcd.for C20H34O4:C 70.33,H 9.94; found:C 70.19,H 9.87.3c:Yield:75%; 1H NMR (300 MHz,CDC13,δppm):0.86-0.90 (m,3H),1.32-1.38 (m,16H),1.47-1.52 (m,2H),1.62-1.68 (m,4H),1.79-1.85 (m,2H),2.13 (m,1H),2.24 (m,1H),2.35 (t,2H,J= 10.5 Hz),2.58-2.61 (m,1H),2.68-2.73 (m,1H),4.05-4.11 (m,2H),4.13-4.20 (m,2H),5.65(s),5.70(s);IR,v:1720,1700,1640; anal.calcd.for C23H40O4:C 72.09,H 10.45; found:C 72.04,H 10.25.3d:Yield:68%; 1HNMR (300 MHz,CDCl3,δ ppm):0.89-0.94 (m,6H),1.32-1.36 (m,12H),1.45-1.57 (m,4H),1.64-1.86 (m,4H),2.10-2.15 (m,1H),2.32-2.37 (m,1H),2.35 (t,2H,J= 10.5 Hz),2.58-2.63 (m,1H),2.68-2.73 (tm,1H),4.05-4.20 (m,4H),5.65 (s),5.70 (s); IR,v:1720,1700,1640; anal.calcd.for C23H40O4:C 72.09,H 10.45; found:C 72.32,H 10.32.3e:Yield:57%; 1HNMR (300 MHz,CDCl3,δppm):0.88 (t,3H,J = 6.0 Hz),1.24-1.36 (m,22H),1.47-1.52 (m,2H),1.61-1.68 (m,4H),1.79-1.86 (m,2H),2.10-2.15 (m,1H),2.24-2.29 (m,1H),2.35 (t,2H,J= 10.5 Hz),2.58-2.63 (m,1H),2.68-2.73 (m,1H),4.05-4.11 (m,2H),4.13-4.20 (m,2H),5.65 (s),5.70 (s); IR,v:1720,1700,1640; anal.calcd.for C25H44O4:C 73.48,H 10.85; found:C 73.22,H 10.45.3f:Yield:60%; 1H NMR(300 MHz,CDCl3,δ ppm):1.28-1.52 (m,20H),1.64-1.89 (m,8H),2.09-2.14 (m,1H),2.23-2.24 (m,1H),2.35 (t,2H,J = 10.5 Hz),2.57-2.59 (m,1H),2.68-2.72 (m,1H),4.13-4.20 (m,2H),4.71-4.80 (m,1H),5.63 (s),5.68 (s); IR,v:1720,1700,1640; anal.caicd.for C23H38O4:C 73.28,H10.12; found:C 73.43,H 9.88.In the 1H NMR spectrum,two singlets atδ 5.60-5.70 stand for the protons of the double bond of Z-and E-isomers respectively.Sum of their relative intensities is equal to one proton.
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