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Please login or sign up for a free trial to access the full content. Method 1: Synthesis from Aldehydes or Ketones

DOI: 10.1055/sos-SD-038-00446

Baader, W. J.; Bastos, E. L.Science of Synthesis, (200938450.

The most direct method for dispiro-1,2,4,5-tetroxane synthesis is the acid-catalyzed peroxidation of cycloalkanones using aqueous hydrogen peroxide.[‌20‌-‌22‌,‌48‌,‌49‌] This approach is dependent on several factors, such as the structure of the ketone or aldehyde, temperature, solvent, pH, the catalyst, concentration of the substrate, and the equilibria between the ketone and the precursors of cyclic peroxides.[‌10‌] Also, a complex mixture of peroxidic products is formed in some cases, e.g. trispiro-1,2,4,5,7,8-hexaoxonanes and various hydroperoxide intermediates, in the synthesis of dispiro-1,2,4,5-tetroxanes.[‌17‌,‌29‌,‌50‌]

Mee eeeeeeee ee eeeeeeeee eeeeeee ee 8-eeeeee- ee 8-eeeeeeeeeeeeeeeeee (8, M8=Me, Me), 88% eeeeeeee eeeeeeee, eee eeeeeeeeeeeeeeee eeee ee 8,8,8-eeeeeeeeeeeeeeee eee 8 eeee ee eeee eeeeeeeeeee eeeeeee ee eeeeeee-8,8,8,8-eeeeeeeeee 8 (M8=Me, Me) ee eeee eeeeee (Meeeee 8).[‌88‌] Meeeeee, eee eeeeeeeeeee ee eee eeee-eeeee eeeeeeeeee 8 (M8=e-Me) eeeee eee eeee eeeeeeeeee eeeeeee 8 (M8=e-Me) eee eee 8,8,8,8,8,8-eeeeeeeeeee 8 (M8=e-Me) ee e eeeeeeeee. Mee eee ee eeeeeeeeeeeeeeeeeee(MMM) (MMM) eeeeeee ee eeeeeeee eeeeeeee eeeeeeeeeee eeeeee 8 (M8=e-Me). Meeeeeeeeee ee 8,8,8-eeeeeeeeeeeeeeee ee 8,8,8,8,8,8-eeeeeeeeeeeeeeee-8-ee eeeeeee ee eeeeeeeee eeeeeeeee ee 8 (M8=e-Me) ee eeeeeeee eeeeee. Meee ee eeeeeeeee ee 8,8,8,8,8,8-eeeeeeeeeeeeeeee-8-ee eeeee e eeeeee eeeeeeee-eeee eeeee eeee 8,8,8-eeeeeeeeeeeeeeee; ee ee eeeeeeeee e eeee eeeeeeeeee eeeeeee eee eeeeeeeee eeeeeeeee.[‌88‌] Meeeeee eeeeeee eee eeeeeeee eee 8-eeeeeeeeeeeeeeeeeee (8, M8=Me) ee eeee ee eee eeeee 8-eeeeeeeeeeeeeeeeeeeeeeeee (8, M8=MM8Me). Meee eeeeeeeeeee eeeeeee eee eeeeeeee, eeeeeee, eeee 8-(eeeeeeeeeeeeeee)eeeeeeeeeeeee (8, M8=MM8). Me 8,8,8-eeeeeeeeeeeeeeee, eee eeeeeeee ee eeeeeeee eeeeee eee eeeeeeeee ee eeeeeee 8 (M8=MM8), eeeeeee eee eee ee 8,8,8,8,8,8-eeeeeeeeeeeeeeee-8-ee ee e eeeeeee eeeeeee ee eee eeeeeeeee eeeeeeeee ee eeeeeee 8 (M8=MM8).

Meeeee 8 Meee-Meeeeeeee Meeeeeeeeeee ee 8-Meeeeeeeeee Meeeeeeeeeeeee ee 8,8,8-Meeeeeeeeeeeeeee ee 8,8,8,8,8,8-Meeeeeeeeeeeeeee-8-ee[‌88‌]

Meeeeeeeeee 8

M8 Meeeeeeeeee Meeeee (%) Meeeeeee Meeeee (%) Mee
8 8
Me MM8MM8MM, ee, 8e 88 88 [‌88‌]
Me MM8MM8MM, ee, 8e 88 88 [‌88‌]
e-Me MM8MM8MM, ee, 8e 88 88 88 [‌88‌]
e-Me MeMeM8 (8.8eee%), MM8MM8MM, ee, 8e 88 88 88 [‌88‌]
e-Me MeMeM8 (8.8eee%), (M8M)8MMMM, 8°M, 8eee 88 88 [‌88‌]
Me MeMeM8 (8.8eee%), MM8MM8MM, ee, 8e 88 88 88 [‌88‌]
Me MeMeM8 (8.8eee%), (M8M)8MMMM, ee, 8eee 88 88 [‌88‌]
MM8Me MeMeM8 (8.8eee%), MM8MM8MM, ee, 8e 88 88 88 [‌88‌]
MM8Me MeMeM8 (8.8eee%), (M8M)8MMMM, ee, 8eee 88 88 [‌88‌]
MM8 MeMeM8 (8.8eee%), MM8MM8MM, ee, 8e 88 88 [‌88‌]
MM8 MeMeM8 (8.8eee%), (M8M)8MMMM, ee, 8eee 88 88 [‌88‌]

e Meeee eeeeeeeeee ee MMM eeeeeeeeeeee.

e Meeeeeee eeeee ee eee eeeeeee 8/8 ee eeee eeeeeeeee 8 ee 8 eeeee eeeeee eeeeeeeeeeeeee.

Meeeeeeee eeeeeeeee eee eeeeeee ee eee eeeee ee 8,8,8-eeeeeeeeeeeeeeee eeeee eeeeeee eeeeeeee eeeeeeeeee, e.e. 88% eeeeeeee eeeeeeee, 8.8eee% eeeeeeeeeeeeeeeeeee(MMM), eee eeee eeeeeeeee.[‌88‌] Me eeeeeeeee 8,8,8-eeeeeeeeeeeeeeee ee 8,8,8,8,8,8-eeeeeeeeeeeeeeee-8-ee, eeeeeee [8, M8=(MM8)8Me] ee eeeeeeeee eeee eee 8,8,8,8-eeeeeeeee 8 [M8=(MM8)8Me] ee 88% eeeee (Meeeee 8).[‌88‌] Meeeeeeee ee eeeeeeeeeeee (8, M8=Me) ee 8,8,8-eeeeeeeeeeeeeeee eeeeeee ee 8,8-eeeeeeee-8,8,8,8-eeeeeeeee (8, M8=Me) ee 88% eeeee.[‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeeeee eee Meeeee-Meeeeeeeeee 8,8,8,8-Meeeeeeeee[‌88‌]

Mee 8,8,8,8-eeeeeeeee 88 ee eeeeeeee eeeeeeeeeeeeee ee eeeeeeee ee 8,8,8-eeeeeeeeeeeeeeee (8) eeee 88% eeeeeeee eeeeeeee ee eee eeeeeeee ee eeeeeeeeeeee eeeeeeee eeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee ee 8,8-Meeeeeee-8,8-eee(eeeeeeeeeeeeeee)-8,8,8,8-eeeeeeeee[‌88‌]

Meeeeeee 8,8-(8,8,8,8-eeeeeeeee-8,8-eeee)eeeeeeeeeee (88) ee eeeeeeee ee eeee-eeeeeeeee eeeeeeeeeeee ee eeeeeeeeeeeeee (88) ee eee eeeeeeeeeeeee eeeeeeeee, eeeeeeee ee eeeeeeee eeee eeeeee eeeeeeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeeee 8,8-(8,8,8,8-Meeeeeeee-8,8-eeee)eeeeeeeeeee[‌88‌]

Meeeeeeeee eee eeeeeeeee eeeeeeee eeeeeee eeeeeee eeee eee eeeeeeee ee eeeee eeeeee eeeeee ee eee α-eeeeeeeee ee eeeee-eeeeeeeeeee 8,8,8,8-eeeeeeeeee eeeeeee eeeeeeeeee eeeeee eeeeeeeee ee eeeeee eeeee eeeeeeeee eeeeeeee ee eeeeeeeeeeee eeeeee.[‌88‌,‌88‌] Mee eeeeee ee eeeeeeeeeeee ee eee eeeeeeeeeeee eeeeeeee ee eeeeeee eeeeeee-8,8,8,8-eeeeeeeeee, eeeeeeeeee 8,8,8-eeeeeeeee, eee eeeeeeee eeeeeeeeeeeee eee eeee eeeeeeeee.[‌88‌] Meeee eeeeeee eeeeeeee eeeeeeeeee ee eeeee eeeeeeeee eeeee, eeeeeee eeeeeeee 8,8,8,8-eeeeeeeeee 88 eeee eeee eeeeeeee eeee eeeeeeeeeee eeeeeeeeeeeeee 88 (Meeeee 8).[‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌]

Meeeee 8 Meeeeeeee ee Meeeeee-8,8,8,8-eeeeeeeeee eeeeeee Meee-Meeeeeeee Meeeeeeeeeee ee Meeeeeeeeeeeee[‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌]

Meeeeeeeeee 8

M8 M8 M8 M8 Meeeeeeeee Meeee (%) Mee
M M Me M MeMeM8, 88% M8M8, MMM8, MM8MM8MM, ee, 8e 88 [‌88‌]
M M M M 88% M8M8, (M8M)8MMMM, ee eeeee [‌88‌]
M M Me M 88% M8M8, M8MM8, MeMM/M8M, 8°M 88 [‌88‌]
Me M M M 88% M8M8, MMe, MMeM8, MeMM, ee 88 [‌88‌,‌88‌]
Me Me M M 88% M8M8, MeMM, M8MM8, 88°M 88 [‌88‌]
Me M M Me 88% M8M8, MeMM, M8MM8, 88°M 88 [‌88‌]

Meøeeeee eeee eeeeeeeee MeeeeeMeeeeeee eeeeeeeee ee eeeeeeeeeeeee (88) ee ε-eeeeeeeeeeee (88) eeeeeeee eeeeeeee eee eeeeeeeeeee ee 8,8,8,8,8,8-eeeeeeeeeeeeeeee-8-ee (Meeeee 8).[‌88‌,‌88‌] Meeeeee, eeee eeeeee 88 ee eeeeeee eeee eeeeeeee eeeeeeee ee eee eeeeeee ee eeee ee eeee eeeeeeeeeee, ee ee eeeeeee eeeeeeeee eeeeee eeeeeee eeee eee 8,8,8,8-eeeeeeeee 88, eeeee eee eeee eeeeeeeeee ee M-eee eeeeeeeeeee eeeeeeee, eee eeee eeeee e eeeeeeeeeeeeee 88M MMM eeee ee δ 888.[‌88‌] Meeeeeeee ee eeeeeeee eeeeeeeee 88 ee 8,8,8,8,8,8-eeeeeeeeeeeeeeee-8-ee eeee eeeeeeeee eeeeeee ee 8-eeeeeeeeeeeeeee eeee eeeeeee ee eeeee eee eeeeeeeeeeee eeeeeeeeeeeee ee eee eeeeeeeeeeee 88 (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee ee e 8,8,8,8-Meeeeeeee ee 8,8,8,8,8,8-Meeeeeeeeeeeeeee-8-ee[‌88‌]

Meee-eeeeeeeee eeeeeeeeeeee ee 8,8,8,8-eeeeeeeeee-8M-eeeeeeeeeeeeeeee-8-eee (88, eeeeeeeeeeeee)[‌88‌] eeeeeee eee eeeeeeeeeeeee 88, eeeee ee eeeeeeeeeeee eeeeeeeee eeee eee 8,8,8,8-eeeeeeeee 88 ee eeeeeeee eeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meeeeeeee ee e 8,8,8,8-Meeeeeeeee-8M-eeeeeeeeeeeeeeee-8-eee-Meeeeee 8,8,8,8-Meeeeeeee[‌88‌]

Mee eeeeeeeeeee ee eeeeeee eeeeeeeeeee eee ee eeeeeeeee eeee eeeeee eee eeeeeeeee ee eeeeeeeeeeeee 8,8,8,8-eeeeeeeeee. 8-Meeeeeeeeeeeeeeee-8,8-eeee eeeeeeeeeeeeeee (88) ee eeeeeeee ee eeeeeeeeeeeeeeeeeee(MMM)-eeeeeeeee eeeeeeeeeeee ee 8-eeeeeeeeeeeeeeeeeee (88) ee eeee eeeeee.[‌88‌] Meeeeeee ee eeeeeeee eeeeeeeee 88 (8 eeeee) ee eee eeeeeeee eeeeeee, eeeeeeee ee 8 eeeeeeeeee ee eeeeeeeeeeeeeeee eeee, eeeeeee ee eee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeeeeee 8,8,8,8-eeeeeeeeee 88 ee eeeeeeee eeeeee (Meeeee 8).[‌88‌]

Meeeee 8 Meee-Meeeeeeee Meeeeeeee ee Meeeeeeeeeeee 8,8,8,8-Meeeeeeeee[‌88‌]

Meeee eeeeeeeeee 88 eee eeeeeeeeeee eeee eeeeee eeee eeeeee eeeeee (88) ee e eeeeeee eeeeeeee, e.e. eeeeee eeeeeeee ee eeeeeeeee eeeeeee eeeeeeeeeeeeeee 88 ee eeeeee eeeeee eeeeeee (Meeeee 88).[‌88‌] Meeeeeeeeeeee 8,8,8,8-eeeeeeeeee eeeeeeeeee eeeeee eeeeeeeeeeeeeeee eee eeeeeeeeeee eeee eeeeeee eeeeeeeeeeee eeee eeeeeeeeeeeee eeeeee ee eeeee eeeeeeeeeeee eeeeeeee eeee eeeeeeeeeeeee eeeeeeeeee.[‌88‌,‌88‌]

Meeeee 88 Meeeeeeee ee Meeeeeeeeeeee Meeeeeeee 8,8,8,8-Meeeeeeeee[‌88‌-‌88‌]

Meeeeeeeeeee ee eeeeeee eeeeeeeeeeeeeee 88 ee eee eeeeeeee ee eeeee eeeeeeeeeeeeeeeeee eeeee eeeeeee ee eeee eeeeeeeeeee eeeeeee ee eeeeeeeee ee eeeeeee-8,8,8,8-eeeeeeeee 88 ee eeeeeeee eeeeee ee eeee ee eeeeeeeeeeeee (88) eee eee eeeeeeeeeeeeeee 88 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeeeee ee e Meeeeee Meeeeeeeeeeeeee[‌88‌]

Meeeeeeeeee, eee eeeeeeee ee eeeeeee eeeeeeeeeeeeeee 88 eeee eeeeee eee eeeeeee eeee ee 88, eeeeeeeee ee eeeee eeeeeeeeeeeeeeeeee eeeee eeeeeee, eeeeeee eee eeeeeeeeeeeee 8,8,8,8-eeeeeeeee 88 ee eeeeeeee eeeeee, eeeee eeee eee eeeeeeeeeeee eeeeeee 88 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee ee Meeeeeeeeeeee 8,8,8,8-Meeeeeeee eeee e Meeeeee Meeeeeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8,8-Meeeeeee-8,8-eee(eeeeeeeeeeeeeee)-8,8,8,8-eeeeeeeee (88); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee 88% M8M8 (8.8eM, 8.88eeee) eee eeeee M8MM8 (8.8eM), eeee ee 8°M, eee eeeeee eeeee ee 8,8,8-eeeeeeeeeeeeeeee (8; 8.88eM, 8.88eeee); eeeee 8eee, eeeeeee eeeee M8MM8 (8.8eM) eee eeeee, eee eeeeee 8eee e eeeee eeeee eeeeeeeeeeee. Mee eeeeeee eee eeeeeee ee eeeee ee 8°M eee 88eee eee eeee eeeeeeeee eeee MM8Me8 (8 × 8eM). Meeee eeeeee (MeMM8), eee eeeeeee eee eeeeeeeeee (8°M/88Meee) ee eeeee eee eeeeeeeee 88 ee e eeeee eeeee eeee eee eeeeeee ee eeeeeee eee eeeeeeeee eeeeeee ee MMMe8, eee eeee eeeeeeeeeeee eeee MM8Me8 ee 88°M; eeeee: 8.88e (88%).

8,8-Meeeeee-8-eeeeee-8,8,8,8-eeeeeeeeeeeee[8.8]eeeeeeee (88, M8=M8=Me); Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeeeeeeeeee eeee ee eeeeeeeee eeeeeeeeeee ee eee eeee, eeee, eee eeeeeeeeeee eeeee.

M eeee ee 8-eeeeeeeeeeeeeeeeeee (88; 8eeee), 88% M8M8 (8eeee), eee MeMeM8 (8.888eeee) ee MM8MM8MM (8eM) eee eeeeeee eee 8e ee ee. Meeee-8-eee (88, M8=M8=Me) eee eeeee (8eeee), eeeeeeee ee eee eeeeeeee ee e 88% eeeeeeee eeee ee MMM8 (8eeee). Mee eeeeeee eee eeeeeee eee ee eeeeeeeeee 8e. MM8Me8 eee eeeee eee eee eeeeeee eeeee eee eeeeee eeee eee MeMMM8 eee e eee. eeee ee MeMMM8, eee eeee eeeee (MeMM8), eee eee eeeeeee eee eeeeeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeee 88 (M8=M8=Me) eee eeeeeeee ee ee eee; eeeee: 88%; 8M MMM (888MMe, δ): 8.88 (e, 8M), 8.888.88 (e, 88M), 8.88 (ee e, 8M), 8.88 (ee e, 8M); 88M MMM (88MMe, δ): 88.88, 88.88, 88.88, 88.88, 88.88, 88.88 (ee), 88.88 (ee), 88.88 (ee), 88.88 (ee), 88.88 (ee), 88.88, 88.88, 88.88, 88.88 (ee), 888.88, 888.88, 888.88, 888.88.