Science of Synthesis

Thomas, A. W., Science of Synthesis, (2007) 31, 356.

A cycloaddition between dimethyl acetylenedicarboxylate and 1-(trimethylsiloxy)buta-1,3-diene gives dimethyl 3-hydroxyphthalate (‌92‌), after the oxidation of the intermediate cyclohexadiene ‌91‌ with either the Jones reagent or with 2,3-dichloro-5,6-dicyanobenzo-1,4-quinone (‌Scheme 33‌). Care should be taken not to heat the intermediate ‌91‌ (for example, in refluxing toluene) since the loss of trimethylsilanol takes place resulting in the formation of dimethyl phthalate.[‌54‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeee 8-Meeeeeeeeeeeeeee eeee Meeeeeee Meeeeeeeeeeeeeeeeeeeee eee 8-(Meeeeeeeeeeeeee)eeee-8,8-eeeee[‌88‌]

Me eeeeeeeee eeeeeeeee ee e eeeee ee M-(8-eeeeeeeeeeeee)eeeeeeeeee ‌88‌ ee eeeeeeee eee eee eeeeeeeee ee Meeeeeeeeee'e eeeee (eeeee-8-eeeeeee-8-eeeeeeeeeeeeeeeeeee-8,8-eeeee) eeee 8-eeeeee-(M)-8-eeeeeeeeeeeeeee-8(8M)-eeee ‌88‌ (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee M-(8-Meeeeeeeeeeee)eeeeeeeeee eeee Meeeeeeeeee'e Meeee eee 8-Meeeee-(M)-8-eeeeeeeeeeeeeee-8(8M)-eeee[‌88‌]

Meeeeeeeeee'e eeeee eeee eeeeee eeeeeeeeeeeeeeee eeee eeeeeeee eeeeeeeeeeeeeeeeeeeeee ee eeee eeeeeeee 8-eeeeeeeeeeeeeeee (‌88‌) ee 88% eeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeee 8-Meeeeeeeeeeeeeee eeee Meeeeeeeeee'e Meeee eee Meeeeeee Meeeeeeeeeeeeeeeeeeeee[‌88‌]

Meee eeee ee eeeeeeeeeeeeee eee ee eeeeeeee ee 8,8-eee(eeeeeeeeeeeeeee)eeeee-8,8-eeeeee (eeeeeeeeeeee eeeeeeee eeee eeeeeeeeee), eeeee eeee eeeeeee eeee eeeeee eeeeeeeeee ee eeeeeee eeeeeeeeeeeeeeeeeeeeee eeeeeee eee eeeeeeee eeeeee ‌88‌ (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeee Meeeee eeee 8,8-Mee(eeeeeeeeeeeeeee)eeeee-8,8-eeeeee eee Meeeeeeeee Meeeee[‌88‌,‌88‌]

‌Meeeeeeeeee 88‌

8-Meeeeeeeee eeeeeee, eeee ee 8-eeeeeee-8-eeeeeeeeeeeeeeeeee (‌88‌), eee eeeeee eeeeeeeeeee eeeeeee eeeeeeeeeeeee eeeeeeeee. Mee eeee eeeeeeeeee eeeeee, eee eeeeeeeeeeee eeeeeeee e eeeeeeee eeeeeee Meeeeeeeeee'e eeeee eee 8-(eeeeeeeeeeeeee)eeee-8-ee-8-eee (‌88‌), eeeeeeee ee eee eeee-eeeeeeeee eeeeeeeeeee ee eeeeeeee eee eeeeeeeeeeeeeee eeee eeee eee eeeeee ‌88‌ (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee 8-Meeeeee-8-eeeeeeeeeeeeeeeeee eeee Meeeeeeeeee'e Meeee eee 8-(Meeeeeeeeeeeee)eeee-8-ee-8-eee[‌88‌]

Me eee eeee eee, eeeeeeeee eeeeeee Meeeeeeeeee'e eeeee eee eeeeee 8-(eeeeeeeeeeeeee)eeeeeeeee-8-eeeee ee 8-(eeeeeeeeeeeeee)eeeeeeee-8-eeeee ee eeeeeeeee eeeeee eeeeeee eeeeeeeee eeeeee ee 8-eeeeeeeeeeee-8-eee (‌888‌, e = 8) ee 8-eeeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eee (‌888‌, e = 8), eeeeeeeeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee 8-Meeeeeeeeeee-8-eee eee 8-Meeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eee eeee Meeeeeeeeee'e Meeee[‌88‌]

M eeee eeeeeee eeeeee ee eeeeeeeeeeee eeeeeee ee ee eee eeeeeeee(MM) eeeeeeee eeeeeeee eeeeeeeeeeeeeeeeee ee 8,8-eee(eeeeeeeeeeeeeee)eeee-8,8-eeeeee eee 8,8-eeeeeeeeee eeeeeeeee. Meee eeeeeeeee eee eeee eeeeeeeeeee eeeeeeee,[‌88‌] ee eeee eeeeee-Meeee–Meeee eeeeeeeee eeeee Meeeeeeeeee-eeee eeeeee.[‌88‌,‌88‌] Meeeeeee ee eee eeeee ee eeeee eeeeeeeeee eee eeeeeeee ee eee eeeeeeee(MM) eeeeeeee eeeeeeee [8+8] eeeeeeeee ee eee 8,8-eee(eeeeeeeeeeeeeee)eeee-8,8-eeeeee ‌888‌ eeee 8,8,8,8-eeeeeeeeeeeeeeeeeee (‌888‌) ee eeee eee eeeeee 8-eeeeeeeeeeeeeeee ‌888‌ (‌Meeeee 88‌),[‌88‌–‌88‌] eee e eeeeeee eeeeeeee eeee 8-eeeeeee[8,8,8-eeee(eeeeeeeeeeeeeee)]-8,8,8-eeeeeeeeee (‌888‌) eee eee eeee eeeeeee ee eeee eeeeee 8-(8-eeeeeeeeeeeee)-8-eeeeeeeeeeeee (‌888‌) (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeee eeee Meeeeeeeeee Meeeeeee eee 8,8,8,8-Meeeeeeeeeeeeeeeeee[‌88‌–‌88‌]

Meee eeee ee eeeeeeeee ee eeee eeeeeeee ee eeee eee 8-eeeeeeeeeeeeeeeeeeeee ‌888‌ eee ‌888‌ eeeeeee eeeeeeeee eeeeeee 8,8-eee(eeeeeeeeeeeeeee)eeee-8,8-eeeeee eee eeeeeeeee eeeeeeeeeeee ee eeeeeeeeeeee, eeeeeeeeeeee (‌Meeeee 88‌).[‌88‌,‌88‌] Meeeeeeeee eee eeee ee eeeeeeee ee eee eeeeeeeeeeeee, eeeeeeeee eeeeeeeeeeee 8-eeeeeeee eeeeeee ‌888‌ eeee eee eeeee ‌888‌; eeeee eeee eeeeeeee eeee eeeeeee eeeeeeee ee eee eeeee ee eeeeeeee eee eeeeeeeeeee 8-eeeeeeeeeee-8-eeeeeeeeeeeeeeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee 8-Meeeeeeeeeeeeeeeeeeee eeee Meeeee eee Meeeeeeeeeeee ee Meeeeee Meeeeeeeeeeee[‌88‌,‌88‌,‌88‌]

Mee eeeeee eeeeeeeeeeee eeeeeee eeeeeeeeee ‌888‌ eeeee eeeeeeeeeeee eeeeeeeeee eeee ee ee eeeeeeee eeee eeeeee eee eeeeeeeeeeeee ‌888‌ ee ‌888‌. Meee, eee eeeee eeeeeeeeeeee (‌888‌) eeeee eeeeee 8-eeeeeee-8,8,8,8-eeeeeeeeeeeeeeeeeeeee-8-eeeeeeeeeee (‌888‌), eeeeeee eee eeeeee (‌888‌) eeeeeee eee eeeeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌88‌] 8,8-Meeeeeeeee eeeeeeeeeee, eeee ee eeeeeee-8,8-eeeee, ee eee eeeeeeee ee eeee eeeeeeeeeeeee ee eeee eeee ee eeeeeeee(MM) eeeeeeee eeeeeeee [8+8] eeeeeeee. Meeeeee, eee eeeeeeeeeeeeee eeeee ‌888‌, eeeeee eeee eeeeee-8,8-eeeee, eeee eeeee eeee eee eeeeee M-eeeeeeeeeeeeeeeeee eeeeeeeeee ‌888‌ ee eeeeee eeeeeeeeeeee ee eeee eeeeee 8-eeeeeee-8,8-eeeeeeeeeeeeeeee (‌888‌) ee 88% eeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeee 8-Meeeeeeeeeeeeeee eeee eee Meeeeeeeeeee ee Meeeee eee Meeeeee Meeeeeeee eeee e Meeeee Meeeeeeeeeee Meeeeee Meeeeeeeee[‌88‌,‌88‌]

‌Meeeee 88‌ eeeee eeee eee eeeeeeeee eeeeeeee(MM) eeeeeeee eeeeeeee [8+8] eeeeeeeee eee ee eeeeeee e eeeee ee eeeeeee ‌888‌ eeee eeeeeeeee eeeeee 8,8-eeeeeeeeee eeeeeeeee ‌888‌ eee eeeee eeeeeeee eeeeeeee ‌888‌. Me eeee eeee eee eeeeeeee eeeeeeeeee eee eeee eeeeeee: eeeeee eeeeeeeee eeee eee Meeee eeee ee eeeeeeeeeeeeeee ee −88 ee 88°M eee 88–88 eeeee.[‌88‌,‌88‌,‌88‌–‌88‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeee eeee Meeeee 8,8-Meeeeeeeee Meeeeeeee[‌88‌,‌88‌,‌88‌,‌88‌]

‌Meeeeeeeeee 88‌

M eeeeeee eeeeeeee ee eeeeeeeee eee eee eeeeeeeeeee ee eeeeeeeeeee eeeee 8-eeee-8-eeeeeeeeeeeeeeee ‌888‌ eeeee 8-(eeeeeeeeeeeeee)-8-(eeeeeeeeeeeeeee)eeeee-8-ee-8-eeee ‌888‌, eeeee eee eeeeee eeeeeeee ee eee M-eeeeeeeeee ee eeeee 8-eeeeee-8-eeeeeeeeeeee. Meeeeee eeeeeeeee, eee eeeee eee eeeeeeee ‌888‌ (M8 = Me) eee ‌888‌ (M8 = Me) (eeeeeeee eeee eeeeeee-8,8-eeeee eee 8-eeeeeeeeeeee-8,8-eeeee, eeeeeeeeeeee), eeeeee eee eeeeeeeeeee 8-eeee-8-eeeeeeeeeeeeeeee ‌888‌ (M8 = Me) eee ‌888‌ (M8 = Me) ee eeeeee eeeeee (‌Meeeee 88‌).[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee 8-Meee-8-eeeeeeeeeeeeeeee eeee Meeeee 8,8-Meeeeeeeee Meeeeeeee[‌88‌]

Me eeeeeeeee eeeee ee 8,8-eeeeeeeeeeeee 8-eeeeeee-8M-eeeeeee[e,e]eeeee-8-eeee eeeeeeeee e eeeeeee ee eeeee eeeeeeee e eeee eeeeeeeee ee eeeeeeee (‌Meeeee 88‌).[‌88‌] Mee eeeeeee eeeeee eeee eee eeeeeeeeee ee eee eeeeeeeeeeee eeee ee 8M-8-eeeeeeeeee-8-eee ‌888‌ ee eeeeeeeee eeee eeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee. Meee eeeeeeeee e eeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee ‌888‌, eeeee eeee eeeeee ee eeee eeee ee-M-eeeeeeeee eeeeeeeeeeee ‌888‌ eee e Meeeeee eeeeeeee. Meee eeee eeee ee eeee eeeeeee eee ee eee eeeeeee ee eeee, ee eeeeeeee ee eeeeeee eeeeeeeee eeeee 8,8-eeeeeeee ee eeee.[‌88‌] Meeee eeeeeeeee ee eee eeeeeee eeee eeeeee eeeeeeeeeeee eeee, e eeee-eeeeee eeeeeeeeeeee ‌888‌ eee ee eeeeeeee ee e eeeee ee ee ee 88%. Meeeeee, eeee eeee eeeeeeeeeeee ee eeeeeee eeeeeeee eeee 8 eeeeeeeeeee ee eeeeeeeeeeeee ee eeeeeeeeeeeeeee e eeeeeeee eeeeeeeeee ee e eeeee-Meeeeee eeeeeeee, ee eeeeeeeeeeeeee eeeee eeeeeeee eee eeeeeeeeeeeeeeeeee eeeee e eeeeeeee eeeee ‌888‌, eeeee eeee eeeeeee eeeeeeeeee ee eeee eee eeeeeee ‌888‌. Meeeeee eeeeeeeee ee 8,8,8-eeeeeeeeeeeeee 8-eeeeeee-8M-eeeeeee[e,e]eeeee-8-eeee eee eeee eeee eeeeeeeeeee.[‌88‌]

‌Meeeee 88‌ Meeeeeeee ee 8-Meeeeee-8M-eeeeeee[e,e]eeeee-8-eeee eee Meeeeee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeeeeeee Meeeeeeee

Meeeeeee 8-Meeeeeeeeeeeeeee (‌88‌); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee 8-eeeeeeeeeeeeeeeeeee-8,8-eeeee (88 eeee) eee MMMM (88 eeee) ee eeeeeee (88 eM), (MMMMMMM: eeeeeeeeee) eeeeeeeeee e eeeeeeeee eeeeee ee eeeeeeeeeeee, eee eeeeee ee 88°M eee 88 e. Meeee eeeeeee ee ee, eee eeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeee eee eeeeeeeeeee eeee eeeeee ‌88‌ (8M MMM). Meeeeeeee ee eeee eeeeee eee eeeeeeee eeeeee eeee Meeee eeeeeee ee 8°M eee 88 eee, ee eeee MMM ee eeeeeee; eeeee: 88–88%; ee 88.8–88°M.

M-(8-Meeeeeeeeeeeeee-8-ee)eeeeeeeee (‌88‌, M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

Meeeeeeeeee'e eeeee (8 eeee) eee eeeee ee eee eeeeee-8(8M)-eee ‌88‌ (M8 = Me; 8 eeee) ee eeeeeee (88 eM) eee eee eeeeeee eee eeeeeeee eee 88 e. Meeee eeeeeee ee ee, eee eeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee ee eee eeeeeeeeeeee eeeeeeeeeeee, eeeee eee eeeeeee eeeeeeee eeee 8.888 M MMe/MMM (8:8; 88 eM) eee eeee eeee eee 8 e ee ee. Mee eeeeeee eee eeeeeee eeee MM8Me8 (88 eM) eee eeeeee ee eeee eeee eeeee (8 × 88 eM) eee 8% ee MeMMM8 (8 × 88 eM) ee eeee e eeeeee eeeeeeeeeee. Mee MM8Me8 eee eeeeeee eee eee eeeeeee eee eeeeeeeeeee ee MMM (88 eM). 8% MeMM (88 eM) eee eeeee eee eee eeeeeee eee eeeeeee eee 88 e ee ee eeee eeeeeeee ee eee, eeeeee eee eeeeee eee eeeeeee, eee eee eeeeeee eeee eeee eeeeeeee eee eeeeeeeee ee eM 8 eeee 8 M MMe. Meeee eeeeeeeeee ee eee eeeeeee eeee eeee MM8Me8 (8 × 88 eM), eee eeeeeeee eeeeeeee eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8); eeeee: 88%.

Meeeeeee 8-Meeeeeeeeeeeeeee (‌88‌):[‌88‌]

M eeee ee Meeeeeeeeee'e eeeee (888 ee, 8.8 eeee) eee MMMM (888 ee, 8 eeee) ee eeeeeee (8 eM) (MMMMMMM: eeeeeeeeee) eee eeeeeeee eee 8 e. Meeee eeeeeee ee ee eee eeeeeee ee eee eeeeeee, eee eeeeeee eee eeeeeee eeee 8.8 M MMe/MMM (8:8; 8 eM) eee MMM, eee eeeeeee ee eeeee eee 88 eee ee ee. Mee eeeeeee eee eeee eeeeee eeee 8% ee MeMMM8 (88 eM) eee eeeeeeeee eeee MMMe8 (8 × 88 eM). Mee eeeeeeee eeeeeeee eeee eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeee eeeeeeeeee eeee eeee Me8M ee eeeeee eee eeeee eeeeeeee; eeeee: 888 ee (88%); ee 888–888°M.

Meeee 8-Meeeeee-8-eeeeeeeeeeeeeee ‌88‌ eeee 8,8-Mee(eeeeeeeeeeeeeee)eeeee-8,8-eeeee eee Meeee Mee-8-eeeeeee; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeee eeeeeee eee ee eeeeee eeeeeee eee eeeeeeeeeee eeeeeeeee. Meeeeeee eeeeeeeeee ee eeeeeeeee, eeeeeeeeee eeee eee eeeeee ee eeeeee ee eee eee ee eee eeeeeeeee.

M eeeeeee ee eee 8,8-eee(eeeeeeeeeeeeeee)eeeee-8,8-eeeee (8 eeee) eee ee eeeee eee-8-eeeeee (8 eeee) eee eeeeee ee 888°M (M8 = Me), ee ee 888°M (M8 = Me) ee e eeeeee eeeee, eee 8 e. Meeee eeeeeee ee ee, eee eeeeeee eee eeeeee eeee eee. ee. MM8Me (88 eM), eeeeeeee eeeeeeeee eeee MMe, eee eee eeee eee eeeeeee eee 88 eee. Meeee eeeeeeeeee ee eee eeeeeeeee eeee eeee Me8M, eee eeeeeee eee eeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MM8Me8).

8-Meeeeee-8,8-eeeeeeeeeeeeeeeee-8-(8M)-eee (‌888‌, e = 8); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee 8-(eeeeeeeeeeeeee)eeeeeeee-8-ee-8-eee (888 ee, 8 eeee) eee Meeeeeeeeee'e eeeee (8.888 e, 8 eeee) ee eeeeee (8 eM) eee eeeeeeee eee 88 e. Meeeeee eeeeeee ee eee eeeee (888 ee, 8 eeee) eee eeee eeeee, eee eeeeeee eee eeeeeeeee eee eeeeeee 88 e. M eeeeeeee eeeeee eeeeeeeee eee eeeeeeeeeeee ee eee eeeee eeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, 88 e, eeeeee/MeMMe 8:8) eeeeeeee eee eeeee eeeeeeee; eeeee: 888 ee (88%); ee 888–888°M.

References