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20.5.12.1.1.1 Variation 1: Direct Esterification of Alk-2-ynoic Acids

DOI: 10.1055/sos-SD-020-01178

Evano, G.Science of Synthesis, (2007201243.

One of the easiest and widely used methods for the preparation of alk-2-ynoic acid esters relies on the direct esterification of alk-2-ynoic acids,[‌3‌‌5‌] whose syntheses are fully described in Section 20.2.9 (see also Section 20.5.1.2). Simple propynoic esters can be prepared by treatment of the propynoic acid with a large excess of an alcohol, but this method is not applicable to more expensive alcohols; in the latter case, activation of the carboxylic acid is preferred. These two methods will be reviewed in this section.

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Meeee 8 Meeeeeeee ee Mee-8-eeeee Meee Meeeee ee Meeeee Meeeeeeeeeeeee[‌8‌‌88‌]

M8 M8 Meeeeeee Meeeeeeeee Meeee (%) Mee
Me Me eeeee M8MM8 MeMM 88 [‌8‌]
Me Me eeeee M8MM8 MeMM, ee 88 [‌8‌]
Me eeeee M8MM8 MeMM, 88°M 88 [‌8‌]
MMe-Me Me eeeee M8MM8 MeMM, 88°M >88 [‌8‌]
MM8 (MM8)8Me eeeee M8MM8 Me(MM8)8MM, eeeeee 8888 [‌88‌]
MM8M eMe eeeee M8MM8 eMeMM, 88°M 88e [‌88‌]
Me Me MMe MeMM, 88°M e [‌88‌]
Me eMe MMMe8 eMeMM, ee, 88eee; eeee eeeeee, 88eee 88 [‌88‌]
8-MeMM8M8 Me MeMM MeMM, eeeeee, 88e 88 [‌88‌]
Me MMM eeeeeee, MeeeMeeee 88 [‌88‌]

e Meee eeeeeeeeee eeee eeeeee eeeeeeeeee ee eee eeeeeeee.

e Meeee eee eeeeeeee.

Meeeeee eeeeeeeeeeeeee eeeeeeee eeee eee eeeeeeee eeeeeeeeeeee eeeeeeeee ee eee eeeee eeeeeeeeeeeeeeeeee eeeee eeeeeee, eeeee eee ee eeee ee eeeeeeeeeeeeeeeee eeeeeee eee eeeeeeeeeee eeeee eeeeeeeeeeeeee, e.e. ee eeee 8 (Meeeee 8).[‌88‌] Meeee eeeeeeeeeee ee eeeeee eeee Meøeeeee eeeee eee, eeee eeeeeeeeeee, eeeeeeee eeeeeee eee ee eeeeeeee eeee eeee eeeeeee. Meeeeee eeeeeeee eeeeeeeeee eeeeeee eeeeeeee ee eee eee-8-eeeee eeee eeee 8.88 eeeeeeeeeee ee eee eeeee eeeeeeeeeeeeeeeeee eeeee eeeeeee ee eee eeeeeeeeeee eeeeeeeee eeeeeee.

Meeeee 8 Meeee MeeeeeeeeeeMeeeeee Meeee Meeeeee Meeeeeee Meeeeeeeeeeeee ee Mee-8-eeeee Meeee[‌88‌‌88‌]

Me eee eee ee e eeeee eeeeee ee eee eeeeeee eee/ee eeeeee eeeeeeeeee ee ee ee eeeeeee, e eeeee eeeeee ee eeeee eeeeeeeeee eee eeeeeeeee. Meeee eeeeeee eeee ee eee eeeeeeeeee ee eee eeeeeeeeee eeee, eeeeeeeeeeee eeeeeeeeeeee eeeeee ee eee eeeeeeee eeeee.

Mee ee eee eeee eeeeee eeeeeeeee eeeeeee eee eeeeeeeeee ee eee eeeeeeeeee eeee eeeeee eeeeeeeeeeeeee ee Meeeeeee'e eeeeeeeee eeeee 8-(eeeeeeeeeeeee)eeeeeeee-eeeeeeeee eeeeeeeeee eeee 8,8-eeeeeeeeeeeeeeeeeeeeeeee.[‌88‌] Mee eeeeeeeeeeeeee eeeeeeee eeeeeee eee eeee eee e eeeeeeeee, eeeeeeeee, eeeeeeeeee eeee eeeeeeeeee, ee eeee eeeeeeeeeee, eeeee eeeeeeeee, eeeeee eeeee eeeeeeeeee. Me eeeeeeee ee eeeeeeeeeeeeeee, eeeee eeeeeee eeeeeeee ee eeeeeeeeee eeeeeeee eeee ee eeeeeee eeeee, eeeeeeeeeeeeeee, ee eeeeeeeeeeee eee ee eeee.

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Meeee 8 ­Meeeeeeeeeeeee ee Mee-8-eeeee Meeee Meeeeeee ee 8,8-Meeeeeeeeeeeeeeeeeeeeeee eee 8-(Meeeeeeeeeeee)eeeeeeee[‌88‌,‌88‌‌88‌]

M8 M8 Meeeeeeeee Meeee (%) Mee
8-MeMM8M8 eMe MM8Me8, ee, 88e 88 [‌88‌]
Me eeeeeee, 8°M, 88eee 88 [‌88‌]
Me MM8Me8, 8°M ee ee, 8e 88 [‌88‌]
Me MM8Me8, ee, 88e 88 [‌88‌]
Me MM8Me8, 8°M ee ee, 8e 88 [‌88‌]
Me MM8Me8, ee e [‌88‌]
Me 8,8-Me8M8M8 MM8Me8, 8°M ee ee, 8e 88 [‌88‌]
8-eeeeeeeee 8-M8MM8M8 MMM, ee, 8e 88 [‌88‌]

e Meeee eee eeeeeeee.

Me eeeeeeee, ee eee eeee eeee eeeee eeee eee eeeeeeee ee e eeeeee eeee eeee ee 8-eeeeeeeeeeeeeee eeee eee eeeeeeeeeeee eeeeeee eee eeeee ee eee eeeeeeeeeeee.[‌88‌,‌88‌] Meeeeee, eee eeeeeeee ee 8,8-eeeeeeeeeeeeeeeeeeeeeeee eee eee eeeeeeeee ee 8,8-eeeeeeeeeeeeeeee, ee e eeeeeeeee ee eee eeeeeeee, eee eeeee eeeeeeeee ee eeee eeeeeeeee eeeeeeeeee eeeeee. M eeee eeeeeeeeeee ee 8,8-eeeeeeeeeeeeeeeeeeeeeeee ee eee eee ee 8-[8-(eeeeeeeeeeeee)eeeeee]-8-eeeeeeeeeeeeeeeee (MMM), eeeee eeeeeeeee e eeeee-eeeeeee eeee[‌88‌] eee eee eeee eeeeeee ee eee eeeeeeeee ee eee-8-eeeee eeee eeeeee.[‌88‌,‌88‌]

Mee-8-eeeee eeee eeeeee eee eeee ee eeeeeeee eeeee eeee eeeeeeeeee ee eeee eeeeeeeeeee ee eee eeeeeeee ee eee-8-eeeee eeeee eeee eeeeeeee ee eee eeeeeeee ee e eeee eee eee(8-eeeeeeeeeeeee-8-ee)eeeeeeeeee eeeeeeee (MMM-Me, 8).[‌88‌] Meeeeeeeeeeeee eeeee eeeee eeeeeeeeee ee eeeeeeeeeeee ee eee eeeeee eeeeeeee eeeeeeeeeeeeeeeee eeeeeeeeeeee 8 ee eee eeeeeee. Meee eeeeee eee ee eeee ee eeee eee-8-eeeee eeee eeeeee, e.e. 8, eeee eeeeeeee eeeeeeee ee eeee eeeeeeee eee-8-eeeee eeeee ee eeee eeeeee eee eeee e eeeeeeeeee eeee (Meeeee 8).[‌88‌] Meee eeeeeee eee eeee eeee eeeeeeeeee eee eee eeeeeeeeeeee ee eeeeeeeee eeeeeee ee eeeeeeeeee eeeee eee eeeeeeee ee eeee eeeeee eee ee eeeeeeee eee ee eee eeee eeeeee eeeeeeee.

Meeeee 8 Mee(8-eeeeeeeeeeeee-8-ee)eeeeeeeeee Meeeeeee Meeeeeee Meeeeeeeeeee ee Mee-8-eeeee Meeee eee Meeeeeee[‌88‌]

Meeeeee eeee eeeeeeeeeeeeee eeeeeeeee, eeeee eee ee eeee eee eee eeeeeeeee ee eee-8-eeeee eeeeee, eeeeee ee 8-eeeeeeeeeeeeee eeeee eeee ee 88 ee 88 (Meeeee 8).[‌88‌,‌88‌] Mee eeeeeeee eeeeeeee ee eeeeeee eeeeeeeee ee e 8-eeeeeeeeeeeeeeeee eeee 8, eeeeeee eeeeeeee ee eeeeeeeeeeee eeeeeeeeeeee ee e eeeeeee eeee, eeeee eeee eeeeee eeee eee eeeee ee eeeeeee eee eeeeee eeeeeee: eee eeeee eee eee M-eeeeeeeeeeee-8-eee 8. Mee eeeeeeeee eee eeeeeee eee ee eee eeeeeeee ee ee eeeee ee e eeeeee eeeeeeee eee eee eeeee ee eeeeeeeee eeeeeeeee ee eee eeeeeeee ee eee eeeee (eeeeeeeeeeeee > 8-eeeeeeeeeeeeee > eeeeeeee). Mee-8-eeeee eeee eeeeee eeee ee 88[‌88‌] ee 88[‌88‌] eee ee eeeeeeee eeeee eeee eeeeeeeee.

Meeeee 8 8-Meeeeeeeeeeeee Meee Meeeeeee Meeeeeeeeeee ee Mee-8-eeeee Meeee eee Meeeeeee[‌88‌‌88‌]

Meeeeee eeeeee ee eeeee ee eee eee ee 8,8,8-eeeeeeeeeeeeeeee eeeeeeee (88).[‌88‌] Meee eeeeeeeee ee eeeeeeeeee eeeeeeee eee eeeeeeeeeeeeeeeeee ee eeeeeeeeee-8-eeeee eeeee (Meeeeeeee'e eeeeeeee). Me eeeeeee ee eeee eeeeeeeee eeeeeee ee eee eeeeeeeee ee 88, ee eeeeeeee eeeeeeeee ee eee eeeee eeeeeeeee ee eeeeeeeeeee, ee eeeeeeee ee Meeeee 8.[‌88‌]

Meeeee 8 Meeeeeeee'e Meeeeeee Meeeeee ee eee Meeeeeeee ee ee Mee-8-eeeee Meee Meeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeee (8-Meeeeeeeeeeee)eeeeeeeeee (8, M8=8-MeMM8M8; M8=Me); Meeeeee Meeeeeeee:[‌88‌]

M eeee ee (8-eeeeeeeeeeeee)eeeeeeeee eeee (8.88e, 88.8eeee) eee MeMM (888ee, 8.8eeee) ee eee MeMM (888eM) eee eeeeeeee eee 88e. Mee eeeeeee eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, M8M eee eeeee, eee eee eeeeeee eeeee eee eeeeeeeee (MeMMe). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee 8% ee Me8MM8 (8 × 88eM), M8M (8 × 88eM), eee eeeee (88eM), eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeee (8888°M/8.88Meee) ee eeeeee eee eeeee; eeeee: 8.88e (88%).

Meeeee 8-{8-[(Meeeeeeeeeeeeee)eeeeeee]eeeeeeeeeee}eeee-8-eeeeee (8); Meeeeee Meeeeeeee:[‌88‌]

M eeee ee 8-[8-(eeeeeeeeeeeeee)eeeeeeeeeee]eeee-8-eeeee eeee (8.88e, 88.88eeee) ee eeeee MeMM (888eM) eee eeeeeee eeeeeeee eeee MM8MMe8 (8.88eM, 88.8eeee) ee 8°M. Mee eeeeeeeee eeee eee eeee eeeeeeee eee 8e, eeeeee ee ee, eee eeeeee eeee eee-eeee 8% ee Me8MM8 (888eM). Mee eeeeeeeee eeee eee eeeeeeeee eeee Me8M (8 × 88eM), eee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee 8% MeMMM8 eeee (888eM) eee eeeee (88eM), eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeeeeeeeee (e-MeMMe) ee eeee eee eeeeeee; eeeee: 8.88e (88%).

8,8-Meeeeeeeeeeeee Mee-8-eeeeee (8, M8=Me; M8=8,8-Me8M8M8); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: 8,8-Meeeeeeeeeeeeeeeeeeeeeee ee e eeeeee eee, eeee, eee eeeeeeeeeee eeeee eeeeeeee, eee e eeee eeeeeeeeee.

Me e eeee ee 8,8-eeeeeeeeeeeeee (888ee, 8.88eeee) ee MM8Me8 (8 eM) eee eeeee eee-8-eeeee eeee (888.8ee, 8.88eeee), MMMM (88.8ee, 8.888eeee), eee e eeee ee MMM (888.8ee, 8.88eeee) ee MM8Me8 (8eM) ee 8°M. Meeee 8e ee ee, eee eeeeeeeeeee eee eeeeeee ee eeeeeeeeee, eee eee eeeeeeee eee eeeeee eeee M8M, eeeee (MeMM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:8) ee eeee eee eeeee; eeeee: 888ee (88%).

[8-Meeeee-8-eeee-8,8-eeeeeeeee-8-(eeeeeeeeeeeeee)-8-eeeeeeee]eeeeee (8M)-8-Meeeeeeee-8-eeeeee (8); Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee [8-eeeeee-8-eeee-8,8-eeeeeeeee-8-(eeeeeeeeeeeeee)-8-eeeeeeee]eeeeeeee (888ee, 8.8eeee), (M)-8-eeeeeeeee-8-eeeee eeee (888ee, 8.8eeee), eee Me8M (8.88eM, 8.8eeee) ee eeeee MM8Me8 (8eM) eee eeeee eee(8-eeeeeeeeeeeee-8-ee)eeeeeeeeee eeeeeeee (8; 888ee, 8.8eeee) ee ee eeeee eeeee. Meeee 88e, eee eeeeeee eee eeeeeeee ee eeeeeeee ee eee. ee MeMMM8 (88eM). Mee eeeeeee eeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeee eeeeee eeee eeeee (88eM), eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee ee eeee eee eeeee eeeeeee, eeeee eee eeeeeeee ee eeeeeeeeeeeeeeeee ee eeeeee eee eeeee; eeeee: 888ee (88%).

References


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