Science of Synthesis

Kanemasa, S., Science of Synthesis, (2004) 19, 31.

Ethyl nitroacetate is a source of three nitrile oxides depending upon the reaction conditions (‌Scheme 18‌). Thermolysis of ethyl nitroacetate in mesitylene results in the elimination of ethanol and carbon dioxide generating formonitrile oxide (‌46‌).[‌78‌] Treatment with 1,3-diisocyanato-4-methylbenzene in the presence of a catalytic amount of triethylamine gives ethoxycarbonyl-substituted formonitrile oxide ‌47‌, while treatment with phenyl isocyanate, together with an equimolar amount of potassium carbonate, affords α-ethoxycarbonyl-α-nitro-substituted acetanilide ‌48‌. This product on thermolysis undergoes the elimination of ethanol and carbon dioxide to form the corresponding nitrile oxide ‌49‌. Each nitrile oxide can be efficiently trapped with alkene dipolarophiles.

‌Meeeee 88‌ Meeeeeeee ee Meeeeee Meeeee eee Meeee Meeeeeeeeeee eeee Meeee Meeeeeeeeeee[‌88‌]

(Meeeeeeeeee)eeeeeee eeee eeeeeee eeee eeeee eeeeeeeeeeeee ee eeeeeee ee eeeeee eeeee M-eeeeeeeeeeeeeeeeeeeeeeeeeeeeee eeeeeeee, eeeee eeeeee ee eeeeee eeeeeeeee eee eeeeeeeeeeee eeeee.[‌888‌] Meeeeeeeeee ee eeee eeeeeeeee ee eeeeeeeee eeeee eeeeee ee eeeeeeee eee e eee eeeee eee eee eeeeeee eeeee eee ee eeeeeee eeee eeeeeeeeeeeeee ee eeee. Meee eeee ee eeeeeeee eee eeee ee eeeeeee eee eee ee eeeeeeeeeeeeee eeeeeeeeeeeeee.[‌88‌] Meeeeeeeeeeee eeeeeee eeeeee eee ee eeeeeeeee eeeee eeee eeeeeeeeee; eee eeeeeee, 8-eeeeee-8-eeeeeeeeeeeee-8(8M)-eee (‌88‌) eeee eeeee ee eeeeeee eeeeeeeeeeee ee eeee eeeeeeeeeee ee eeeeee eee eeeeeee eeeee ‌88‌, eeeee eeee eeeee eeeeeeeeeeee eeee eeeeeeeeeeeeee, eeee ee eeeee eeeee eeeee ee eeeeeeeeeeeeeee, eeeeeee ee eee eeeeeeee (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeeee ee e Meeeeeeeeeeee Meeeeee Meeee eeee e 8-Meeeeeeeeeeee-8(8M)-eee[‌888‌]

Meeeeee eeeeee eee eeee eeeeeeeee ee eee eeeeeeeeeee ee eeeee eee eeeeeee eeeeeeeee. Meee, eeeeeee 8-eeeeeeeeeeeeeee ee eeeeeeeee ee ee. 888°M eeeeeeee eeeeeee eeeeee, eeeee eee ee eeeeeee ee eeee ee eeeeee ee eeeeee eeeeeeeeeeeeee.[‌888‌] M-(eeee-Meeeeeeeeeeeeeeeee)eeeeeeeeee eeeee ‌88‌ eeeee ee eeeeee, eeeeeee eeeeeeeeee, eeeeeeeeeee eeeeeeeeee eee eee eeeeeeeeee ee eeeeeee eeeeee;[‌88‌] eeee eee ee eeeeeeee eeeeee eeee eeee eeeeeeeee ee eee eeeeee ee M-(eeee-eeeeeeeeeeeeeeeeee)eeeeeeeeeeeee ee eeee eeeeeeeeee eeeee eee M-eeee-eeeee(eeeeee)eeeeeeeeeeeeee. Meee eee M-(eeee-eeeeeeeeeeeeeeeeee)eeeeeeeeee eeeee eee eeeeeee eeee eeeeeeeeeeeeeeeeeeeeeeee eeeeeeeee eee eeeeeeeeeeeee ee eee eeeeeeeeeee eee eeeeeeeeeeeee M-eeeeeeeeeeeeeeeeeeeeeeeeee ‌88‌ eee eeeeee ee eeeeeeeeeeeee eeee eeeeeeeee ee eeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeeee. Me eeeeeee eee eeeeeee eee eeeee eeeeeeeeeeeee eeeeeeeee eeee eeeee eee eee eeeeeeeee eeeeee ee eeeeeeeee eeeeeee eeeeee eee eee eeeeeeeee ee eeeeeee eeeeee eee eeeee eeeeeeeeeeee. Mee eeeeeee, eeeeeeeeee eeeeeee eee eeeeee ‌88‌ ee 88% eeeee eeee eee eeeeeeeee eeeeeeeee ‌88‌ (M8 = Me) (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeee Meeeee eeee M-eeee-Meeeeeeeeeeeeeeeee-Meeeeeeeeee Meeeeeeeee Meeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

M-(eeee-Meeeeeeeeeeeeeeeeee)eeeeeeeee (‌88‌, M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Meeeeeeeeeeeeee eeee (M-eeeeeeeeeeeeeeee) (8.88 e, 8.8 eeee) ee MMM (8 eM) eee eeeee eeeeeeee ee 8°M ee e eeeeeeeeee ee MeM (8.88 e, 8.8 eeee) ee MMM (8 eM). Mee eeeeeeeee eeeeeee eee eeeeeee ee eeee eeeeeeeeeee eee e eeeeeee 8 eee, eee eeee eeeeeee eeee MMMMMMe (8.88 e, 8.8 eeee). Meeee eeeeeeee eee ee eeeeeeeeee 88 eee, eee eeeeeee eee eeeeeeeeee eeeeeee eeee eeeeeee MeMM (8 eM) eee eeeeeee ee eeee ee ee. Me eee eeeeeeeeeeee eeeeeee eeee M8M (88 eM), eee eeee eeeee (Me8MM8). Meeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee eeee e eeeeeeeee eeeee. Meeeeeeeeeeeeee (Me8M/eeeeee), eeeeeeeeeee ee eee eeeeeeee, eee eeeeeeeeeeeeeeeee ee eee eeeeeeee eeeeeeee eeee eee eeee eeeee eeeeeeee; eeeee: 8.8 e (88%); ee 888–888°M.

M-(eeee-Meeeeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeee (‌88‌, M8 = MM8MM8Me); Meeeeee Meeeeeeee:[‌88‌]

MMMe8 (8.8 eM, 88 eeee) eee eeeee ee 8-eeeeeeeeeeeeeee eeee (8.8 e, 88 eeee) eee Me8M (8.8 eM, 88.8 eeee) ee MMM (888 eM) ee 8°M, eee eee eeeeeee eee eeeeeee ee 8°M eee 88 eee, eeeeee M-(eeee-eeeeeeeeeeeeeeeeee)eeeeeeeeeeeee (8.8 e, 88 eeee) eee eeeee. Mee eeee eeeeee eeeeeee eee eeeeeee eee 8 e, eeee eeeeee eeee MeMMe (888 eM), eee eeeeee eeee eee. ee MeMMM8, eee eeee M8M. Meeee eeeeee (Me8MM8), eee eeeee eeeee MeMMe eeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeeeeeee eeeee eeee eeeeee. Meeeeeeeeeeeeeeee (Me8M/eeeeee) eeee e eeee eeeeee eeeee; eeeee: 8.8 e (88%); ee 888–888°M.

M-(eeee-Meeeeeeeeeeeeeeeeee)-8-eeeeeeeeeeeeeeeee (‌88‌, M8 = MM=MMMe):[‌88‌]

8 M MMM ee MeMM (88 eM, 888 eeee) eee eeeee eeeeeeee ee eeeeee eeeeeeeee (8.8 e, 88 eeee) eee MM8MM•MMe (8.8 e, 88 eeee) ee MeMM (88 eM). Meeee eeeeeeee eee 88 e ee ee, eee MeMM eee eeeeeeeeee ee eeee e eeeee. Meee eee eeeeeeeeeee ee MeMM/M8M (8:8, 88 eM) eee eeeeeeeee eeee MeMMe (8 × 88 eM). Meeee eeeeee (Me8MM8), eeeeeeeeeeeee ee eee eeeeeeee eeeeeeee eeeeeeee ee eee. Meeee eeeeeeeeee eeeeeeeeeee eeee eeeeeee (8 × 88 eM) eee MeMM (8 × 88 eM), e eeeee eee eeeeeeee, eeeee eee eeeeee eeee Me8M ee eeee M-eeeeeee-8-eeeeeeeeeeeeeeeee (8.8 e, 88%) ee eeeee eee eeeeeeee; ee 888–888°M. Mee eeeeeeeee eeeeeeeeee eee eeeeeeee ee eeeeeeee eeee eeee (8.8 e, 88 eeee) eeee MeM (8.8 e, 88 eeee) eee MMMMMMe (8.8 eM, 88 eeee) ee MMM (88 eM) ee eeeeeeeee ee eee eeeeeeee eeeeeeeeee. Meeee eeeeeeeeeeeeeee (Me8M/eeeeee) eee eeeee eeeeeeee eee eeeeeeee ee e eeeee eee eeeee; eeeee: 8.8 e (88%); ee 888–888°M.

8-Meeeee-8e,8,8,8,8,8e-eeeeeeeee-8,8-eeeeeee-8,8-eeeeeeeeeeeee (‌88‌):[‌88‌]

88% Me8M (8.88 eeee) ee MM8Me8 (8.88 eM) eee eeeee eeeeeeee ee M-(eeee-eeeeeeeeeeeeeeeeeee)eeeeeeeee (‌88‌, M8 = Me; 8.888 e, 8.88 eeee) eee Me8M (8.888 eM, 8.88 eeee) ee MM8Me8 (8 eM) ee −88°M. Meeee eee eeeeeeee, eee eeee eee eeeeeee ee eeee ee 8°M eee 8 e, eee eeee eeeeeeeeee (8.888 e, 8.88 eeee) eee eeeee. Mee eeeeeee eee eeeeee ee ee, eee eeeeeee eee 8 e, eee eeee ee eee eeeeee eeee M8M (8 × 8 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeeeeee eeee MeMMe (8 × 8 eM), eee eee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (8 eM), eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8) eeee e eeeeeeeee eeeee; eeeee; 8.88 e (88%); ee 88°M.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) M 8-8, 8888.
• 8.Meeeee-Meee, (8888) M 8e, 888.
• 8.Meeeee-Meee, (8888) M 8e, 888.