Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content.
1.9.2.1 Carbonylation Using Monophosphine Ligands

DOI: 10.1055/sos-SD-201-00223

van Leeuwen, P. W. N. M.Science of Synthesis: Stereoselective Synthesis, (20111437.

For the highly efficient methoxycarbonylation of propyne, Drent and Budzelaar discovered that an excellent ligand is 2-diphenyl(2-pyridyl)phosphine,[‌118‌] which was used earlier for alkene/carbon monoxide oligomerizations.[‌119‌] Although the ligand most likely functions in a bidentate manner, it is a monophosphine and therefore will be discussed in this section. Other monophosphines studied extensively, such as triphenylphosphine and trisodium tris(3-sulfonatophenyl)phosphine (TPPTS) give less interesting results. The reaction transfers a low-value cracker product propyne into valuable methyl 2-methylacrylate. Methyl substitution at the 6-position of the pyridyl group makes the catalyst even more selective. The catalyst works under very mild conditions and product and catalyst can be separated by distillation. Shell studied the reaction in a bench-scale unit but the process did not reach commercialization, most likely because the availability of pure propyne on the required large scale, in one refinery site, is limited.

Mee eeeeeeee eeee eeeee eeee eeee eeee eeeeee eeeeeee eee ee eeee eeeeeeee eee eeeeeeee eeeeee 88 ee eeeeeeee ee eee eeee eeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeeeeeeeeeeeee ee Meeeeee[‌88‌]

Meeeeee-eeeeeeeee eeeeeeeee eeee eeee eeeeeeee eee eeee eeee eee eeee eeeeeeeeeeeee eee eeee eeeee ee eeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeee.[‌888‌]

Meee eee eeeeeeee eeeeeee ee eeeeeeee, eeeee eeeeeeeee eeee eeee eeeeeee ee eeeeeeeeeeeeeeeeeee. Mee eeeeee, eeee eeeeeee eeee eeeeeeeee eeeeeeeee eee eeee- ee eeeeeeeee eeeeeeeee eeeeeeeee, eeee eee eeeeee eeeeeee eee M8=eeeee. Meeeeeee eeeeeeeeeee, ee eee eeeeeee-eeeeeeeee eeeeeeeeeeeeeeee, eeee e eeeeeeee ee eeee eee eeeeeeee eeeeeee, eee eee eeeeeeeee eeeeeee eeee ee eee ee eeeeeeeeee eee eeee eeeeeeeeeee, ee eeeeeeeee eeeee. Mee eeeeee eeeeeeeeeeeee eeeeeeee eeeeeeee ee eeeeeee ee eeeee eeee eee eeeeeeeee ee e eeeeeeeee eeeeeeeeeeeeeee eeeeeee, eeee eeeee eee eeeeee eeeeeee eeee eee eeeee eeeee eeeeeeee ee eee eeeeeeeeeeeeeee eeeee eeeeee eeee ee eee eeeeeeeee ee eee eeeeee.[‌888‌‌888‌] Meeeeee eee ee-eeeeeee eeeeee eeee ee e eeeeeeeeeeeeee eeeeeee eeeeeeeeeeeeeeeeeeee eee eee eeeeeeeee eeeeeeeeeeeeeee eeeeeee ee eeeeeeee,[‌888‌] eee eee eeee ee eeee eee eee eeeeeeeeeeeeeeeeeee ee eeeeeee. Meeeeeeeeeee, eeeeeeeeeeeeeeeeeee ee eeeeeee eeeeeeee eeeeee eeee eee eeeeeeeee ee eee eeeeee eeee eee MeM eeee (eee Meeeeee 8.8.8, Meeeee 88); eeeee, eee eeeeeeeee eeeee eeee ee M8, eeee eeeeeee eee eeeeee eeeee.[‌888‌‌888‌] Meeee eeeeeeeee eeeeeeeeee, e.e. ee eee eeeeeeee ee eeeeeeee, eee eeeeeeeee eeeeeee eeeeeeeee, ee eeeeee, ee eeeeeeeeeeee eeeeeeee eee eee eeeeeeeee eeeeee eeeee eeee eee eeeeeeeee ee e eeeeeeeeeeeeeee eeeeeee; ee eeee eeee, ee eeeee-eeeeeee eeeeeeee eeeee e eeeeeee.[‌888‌] Meeeeeeee eee ee-eeeeeee eeee eeeeeeeee eeeeeeee eeee eeeeeeeeeeeeeeeeeeee ee eeeeeee eeeeeee eeee eeeeeeee eee eee eeeeeee eeeeeeeee eeee eeeeeeee(eeeeeee)eeeeeeeee ee eeee.[‌888‌]

Meeeeeeeeeeeeeeeeeee ee eeeeeeee eeeeeee ee e eeeeee eeeeeeee ee eeee-eeeeeeee eeeeeeeee ee eee eeee eeeee ee Meeeeeeee eee ee-eeeeeee, eee eeeeeeeeeee eeee 88, e eeeeeeeee ee eeeeeeee, ee eeee eee (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeee ee e Meeeeeee Meeeeeeee ee Meeeeeeeeeeeeeeeeeee ee ee Meeeee[‌888‌]

Meeeeeeee eee eeee eeeeeeee ee eeee eeeeee Meeeeeeeee (88),[‌888‌] e eeee-eeee eeeeeeee eeee eeeeeeee ee M eeeeeeeeeeeee ee M8, eeeee M8 eee ee eeeeee M ee M. Meeeee 88 eeeee ee eeeeeeee ee eee eeeeeeeee. Mee eeeeee eeeeee ee M8 ee eeeeeeee eee eeeeeeeeeeeee (Me/MMMMM), eeeeeee ee eee eeeee eeeeeeee ee Meee eee eee eeeeeeeee ee (M)-eeeeeeee.[‌888‌,‌888‌]

Meeeee 88 Me Meeeeeeeeee ee eee Meeeeeeeeeeeeeeeeeee ee Meeeeee[‌888‌]

Meeeeeeee eeeeeeeee/eeeeeeeeeeeeeeeee/8-eeeeeeeeeeeeeee eeee eeeeeeeee eeee eeee eeeeeeeeeeeeeeee eee eee eeeee eee 8888% ee eee eeeeeeee eeeeee ee eeeeeeeeeeeeeeeeeeee ee eeeeeee (88eee MM, MeMM, 88°M),[‌888‌] eeeee e eeeeeeeee eeeeee eeee ee 8,8-eee(eeeeeeeeeeeeeeeee)eeeeeeeee eeeee 8888% ee eee eeeeeeee eeeee. Meeeeeee ee eeeeee(MM) eeeeeeee ee eee eeeeeeeeeeeeeeeeee eeeeeeeee eee eeeeeeee eee eeeeeeeeeee eee eeeee (88%) eee eeeeeeeeeeeeeeee (88%) eee eee eeeeeeee eeeee eeee eeeeeee.[‌888‌] Meeeeeeee eee Meeeeee eeee eeeeeeee eeee eeeee eeeeeeee/eeeeee eeeeeee eeeeee (8888% eeeeeeee) eeeee eeeeeee eeeeeeeeee, eee eeeee eeee eeeeeeee-eeeeeeeeeee eeeeee ee eeeeeeeeeeeeeeeeee eeee ee eeee-eeeeee eeeeee eee eeeee eee eeeeeeee eeeeeee ee 88%.[‌888‌] Meeee eeeeeee ee eeeeeeeeee eee eeee eeeeeee eeee e eeeeeee eeeeeeeee ee eee eeeeeeeeeee. Meee eeeeee ee eeeeeeee eeeeeee ee eeeeee eeeeeee (e.e., 88/88) eee eeee ee eeeeeeee ee eee eee ee eeeee eeeeeeeeeee eeeeeeeeee, eeee ee 8888, eee eeeeeeeeeeeeeeeeeeee eee eeeeee eee. Meeeee 88 eeeee eeee eeeeeee eeeeeeee ee eee eeee eeeeeee eeeeeeee ee eee.[‌888‌‌888‌]

Meeeee 88 Meeeeeeeeee Meeeeeeeee ee Meeeeeeeee Meeeeeeeeeeeeeeeeeee ee Meeeeee[‌888‌‌888‌]

Meeeeeeeeee 88

Meeeee Meeee (88/88) ee (%) ee 88 Mee
88 88:8 88 [‌888‌]
88 888:8 88 [‌888‌]
88 88:8 88 [‌888‌]

Meeeeeeeeeeee(8-eeeeeeeeeeeeeee)eeeeeeeee eeeeeeeee eee ee eeee ee eeeee eee eee eeeeeeeeeeeeeeeeeeee ee eeeeeee, eee eeeeeee eeeeeeeee eeeeeee [eeeeeee, eeeeeee eeeee (eeeeeeee/eeeeee) ~8:8] eee eeeeeeeeeee [eeeeeee, eeeeeee eeeee (eeeeeeee/eeeeee) 8:8] eeee eeeeeeeeeeeee eeeeee ee eeeeeee eeeeeeeeeeee.[‌888‌,‌888‌]

M eeeeeeee eeeee ee eee eeeeeeeeeeeee M-(eeeeeeeeeeeeeeeee)eeeeeee-8-eeeee, eeeeeeeee(MM) eeeeeeee, eee eeeeeeeeeeeeeeeeee eeeee eeee eeeeeeeeeee eee eeeeeeeeeeeee eee eee eeeeeeee eeeee ee eee eeeeeeeeeeeeeeeeeeee ee eeeeeee (Meeeee 88).[‌888‌] Meeeeeee eee eeeeee, eee e eee eeeeeee eeeeeee, eee eeeeeeeeeeeeee, eeee eee eeeeeeeee M,M-eeeee eeeeeee. Mee eeeeeeee ee 8 eeeeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeeeeeeee eeeeeeee eeee eee eeeeeeeeeee. Mee eeee eeeeeee ee eeeeeee eeeeeeeeee 88% eeeeeeee, eeee e eeeeeeee, eee e 88-eeee eeeeee ee 8-eeeeeeeeeeeeeee eeee ee eeeee. Me 88°M eee 88eee ee eeeeee eeeeeeee, eee eeeeeeeeee eeee eeeee ee ee eeee ee 88%, eeee e eeeeeeeeeee eee eeeeee 8-eeeeeeeeeeeeeeee (88) ee 88% eee e eeeeeeee eeeeeeeee ee 88eee·eee8·e8. M eeeeeee eeeeeeeee ee eeeeeeeee eee eeee eeeeee.

Meeeee 88 Meeeeeeeeeeeeeeeeeee ee Meeeeee eeee e M,M-Meeee Meeeeee[‌888‌]

Me eeee eeeee, eeee eeee eeeee eee eeeeeeeeeeeee ee eeeeee eee eeeeeee eeee eeee eeeeeeee, eeeeeee eee eeeee eeeee eee eeeeeee eeee eeeeee eeee eeee eeeeee. Meeeeeeeeee ee eee π-eeeeeeee eeeee eeee eeeeeee eeee eeeeeeee eeeeee eeeee eeeeeeeeeeee, eee eeeeeeeeee ee ee eeee eeeeeee eeee eeeeee eeeeeeeee eeeeeee.[‌888‌] Mee eeeee eeeeeee ee eeeeeeee eee eeeeeeeee ee eee eeeeeeee eeeeeeeeeeee eeeeee eeeeee eeeeeeee eeeeeeeee. Me Meeeeee 8.8.8.8, eeeeeeee eeeeeeeee eeeeeeeeee, e eee eeeeeeee eee eeeee eeeeeeeeee eeeeeeeeeee ee eee eeeee eee eeeeeee; ee eee eeeeeee eeeeeee eee eeeeeeeeeeee eeee ee eeeeeeee ee eeeeee eeee (MeMM, MMe, ee MeMM/MeMe, ee eeeeeee MeMe8), eeeee ee eeeeeeeeee eeeeeeeee ee eeeee, e.e. ee eeeeeeeeeeeeeeeeeeee, eeee ee eeeeeeeee.

Mee eeeeeeeee eee eeeeeeeeeeeeeeeeeeee ee eeeeeee ee eeeee eeee e eeeeeeeee(MM) eeeeeeee/eeee(8-eeeeeeeeeeeeeee)eeeeeeeee eeeeeeee eee eeeee 8-eeeeeeeeeeeeeee eeee, eeeeeee 88888eee eee 8888°M, eee eeee eeeeeee.[‌888‌] M eeeee eeeeee ee 8-eeeeeeeeeeeeeee eeee ee eeeee (88% ee eeeeeee) eee ee ee eee eeeee eeeeeee e eeeeeeeeeee eeeeee ee eeeeeeee. Meeeeeeeeee (eeeeee 88%) eee eee eeeeeeeee ee eeeeeeee eeee eeeeee ee eee eeeeeeeeeeee, eee ee eee eeeee. Meeeeeeeee eeeee eee eeeeeeee ee 88°M (eeeeeeee eeeeeeeee 888eee·eee8·e8) ee eee eeee ee eee eeeeeeeeee ee eeeeeeee eeeeeee, eeeee eeeee ee 88%. Meeeeeeeeeee eeee ee eeeeeeee eeeee eeeee eeeee. Mee eeeeeeee eeeeeeee eeeee e eeeeeee eeeeeeeee eee eeeeeeee eeeeeee ee eeee eeeeee eee eeeeeeee eeeeeee. Meeeeeeee ee eeeeeee ee eee MeM eeee eeeee ee ee η8-eeeeee eeeeeeee. M eeee eeeeee eeeeeeee eeeeeeee eeeee e eeeeeee eeeeeeeeee eee eee eeeeeeee eeee eeeeeeeee ee eee eeee eeee. Me eeeeeeee eeeeeeeeeeee eee eeeeeeeeee ee eee eeeeeeee eeee eeeeeee ee eeeeee eeee eee eeeeeeeeee eeee eee eeeeeeeeeeeeeeeee eeee eeeeee eeeeee eeee eeeeeee.[‌888‌] Mee eeeeee eeeee eeeeeeeeeeee eeeeeeeee e eeee eeeeee eeeeee eeeeeeee eeeeeeeee,[‌888‌] eeeee eeeeeeee eee eeeeeeeee ee eeeeee eeee ee eeeee eeee eeeeeeeee eeeeeeeeeeee eee eeee (eeee eeeee).

Mee eeeeeeeeeee 8-eeeeeeeeeeeeeee eeee eee eeeeeee eeeeeeee eeee eeeeeeeeee ee Meeeeeeee[‌888‌,‌888‌] eee eeeee ee eee eeeeeeeee eeeeeeee eeeeeeeeeee(eeeeeeeeeeeeeeeee)eeeeeeeee(MM). Mee eeeeeee eee eeeeeeeeee eeeeeeee ee eeeee eeeeeeee eeeeeeee; eeee eeee eeeeeeeeeeeeeeee (ee ee 88.8%) eee eee eeeeeeee eeee 88 eee eeeeeeeeeeeee eeeeeeee eeeeeeee eeeeeeeeeee (ee ee 8888e8) eee eeeeeeee eeeee eeeeeeee eeeeeeee eeeeeeeeee (888°M, 88eee) ee eeeeeeee ee eeeee eeeeeee (Meeeee 88). Meeeeeeee(8) eeeeeeeee [eeee ee Me(MMe8)8 eee Me(eee)8] eee eeee ee eeee ee eee eeeeeeee eeeeeeeeee. Meeee eeeee ee e eeeeeeee eee eeeee eee eeeee eee eeeeeee, eeeee eeeeeeee eee eeeeeeeee; eee eeeeeee eeeeee eeee eeeeee eeeee eeeeee ee e eeeeeeeeee eeeeeee[‌888‌] eeeeeeee, eee eeee-eeee eee ee eeeeee eeeee, eeeeeeeee eeeeeee eee eee ee eee eeeeeee ee eeeeee. eeee-Meeeeeeeeeee eeeeeee eee eeeee eee eeeeeeeeeeeee eeee eeeeeeee. Mee eeeeeeeeeeeeeeeeee eee eeeeeeee ee 88 eeeee eeeeee eee eee eeeeeeeeeee eee eeeeeeee eeeeeee ee eeee 88%. Mee eeeeeeeee ee (8-eeeeeeeeeee)eeeeeee ee eeeeeeee eeeeee eee eeeeeeee, eee ee ee eeeeeee eeee eee eeeeeeee eeeeeeee eee eeeeeeee eeeeee eeee eee eeeeee eeeeeeee eeee eeeeeeeee.

Meeeee 88 Meeeeeeeeeeeeeeeeeee ee Meeeeee ee eee Meeeeeee ee 8-Meeeeeeeeeeeeee Meee eee Meeeeee Meeeeeee[‌888‌]

Me eeeeeeeeeee ee eee eeeeeeeeeeeeeeeeeeee ee eeeeeee eeeeeeeeeee ee eee eeeeeeeeeeeeeeeeeeee ee (8-eeeeeeeeeee)eeeeeee eeeeeeeeeee, eeeee ee eeeeeeee eee Meeeeeeee eeeee ee eeeeeeee.[‌888‌] Me Meeeeeeee eeeeeeeee eee eee eeeeeeeeeee ee eeeeeeeee (88) ee eeeeeeeee eeeee eee eeeeeeeeeee ee Meeeee 88. Meeeeeee, 8-eeeeeeeeeeeee eee ee eeee ee eee eeeeeeeee, ee ee eee Meeeeee eeeeeee eee eee eeeeeeeee ee eeeeeeeee.[‌888‌] Mee Meeeeeeee eeeeeee eeee eeeeee eeeeeeeeeeeeeeeeeeeeeeeeeee ee eee eeeeee, eee eee eeeeeee ee eeeeeee eee e eeeeeeeee eeeeeeeeee ee eee eeeeeeeeeee ee eeeeeee. Mee eeeeeee eeeeeeee eeeeeeeee ee eee eeeeeee eeeeeeee ee 888eee·eee8·e8, eee eee eeeeee eeeeee eee ee eeeeee.

Meeeee 88 Meeeeeeeeee ee Meeeeee Meeeeeeee eeee 8-(8-Meeeeeeeeee)-8-eeeeeeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeee Meeeee Meeeeeeee 88; Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

MeMM (8.8eee%) eee eeeeee eeee eeeee ee e eeee ee Me(MMe)8 (8.88eee%) eee eeeeeeee(8-eeeeeee)eeeeeeeee (8.8eee%) ee eee MeMM. Mee eeeeeee eee eeeeeeeeeee ee ee eeeeeeeee eee eeeeeee eeeee MM (8MMe) ee 88°M eee 8e. MMM eeeeeeeeeeee eeeeee eeeeeeee eeeeeeeeee ee eeee eeee. Mee eeeeeee eee eeeeeee eeee Me8M, eeeeee eeee eee. MM8Me eeee eee M8M, eeeee (MeMM8), eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeeee eeeee eeeeee ee eeee eee eeeeeee eeeeeeee; eeeee: ee. 88%. Meee eee ee ee eeeee eee ee eeeeeee eee eeeeeeee(8-eeeeeee)eeeeeeeee; eeeee, eee eeeeeeee eeeeee eee eeeeeeeeeeeee eeeee eee eeeeeeeeee.

8-(8-Meeeeee-8-eeeeeeee)eeeeeee Meee (88):[‌888‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

Mee eeeeeeeeeeeee eeeeeeeee eeeeeeee ee e eeeeeeeeeeee eeeeeee 888-eM eeeeeeeee eeeee eeeeeeeee. Mee eeeeeee eee eeeeeee eeee MMM ee MMM (88eM), eeeeeeee(8-eeeeeee)eeeeeeeee (888ee, 8.8eeee), Me(MMe)8 (8.8ee, 8 8888eeee), 8-eeeeeee-8-eeeeeeeeeeeeeeeeee (8e, 88.8eeee), M8M (8e, 88eeee), eee MeMM (888ee, 8 8eeee), eeeeeeeeeee eeee MM (88eee), eee eeeeee ee e eeeeeeeeeeee eeee ee 88°M. Mee eeeeeeee ee eee eeeeeeee eee eeeeeeeee ee eeeeeeeee eee eeeeeeee ee eee eeeeeeee ee eee eeeeeee. Meeee eee eeeeeee eeeeeeee eeee (88e), eee eeeeeee eee eeeeee eee eee eeeeeeee eee eee eeeeee. Mee eeeee eeeeeee eeeeeeee eeee eeeeeeee ee MMM ee eeeeeeeee eee eeeeeeeeee eee eee eeeeeeeeeee ee eee eeeeeeee. MMM eee eeeeeeeee ee eee eeeeeeee eeeeee, eeeee ee eee eee ee eee ee eeeeeee eeeeeee eeeee eeeeeee eeeeeeee (eeeeee eeeeeeeeee) ee eeee ee eee, eeee eeeee eee eeeeeee eeeeeee eee ee eeeeeeee ee eee eeeee eeeeee. MM eeeeeeeeeee eeeeeeeee ee eeeeeeeeeeeee eeeeeeeeeeee eeeeeeeeee ee eee eeeeee; eeeee: 88%. Mee eeeeeeee eeee eeeeeeeee eeeee 8eee ee MM, eeeeee 88% eeeee ee 88e.

8-Meeeeeeeeeeeeee Meee (88); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

Mee eeeeeeeeeeeee eeeeeeeee eeee eeeeeee eee ee e Meee Meeeeeeee M eeeeeeeee (88eM). Me e eeeeeee eeeeeeee, eeeeeee (88.8eeee), MeMe8(MMe8)8 (8.888eeee), MeMe/MeMM (8.8eeee), M8M (88eeee), eee eeeeee eeeee eeeeee (88eM) eeee eeeeeee ee eee eeeeeeeee. Mee eeeeeeee eeee eeeeeee e eee eeeee eeee M8 eeeeeeee ee MM eee eeeeee ee eee eeeeeee eeeeeeeeeee. Meeee eee eeeeeeeeeee eee eeeeeeee (888°M), eee eeeeeeeee eee eeeeeeeeeee eeee MM (88eee) eee eee eeeeeeee eee eeeeeee ee eeeeeeeee (8888 eee). Me eeeeeeee eee eeeeeeee ee eee eeeeeee, MM eee eee eeeeeee e eeeeeeee-eeeeeeee eeeeeeeee eeee e eeeeeeeee eeeeee. Mee eeeeeeee eeee ee eee eeeeeeeee eeeeee eee eeeeeeee ee eeeee ee e eeeeeeee eeeeeeeeee. Mee eeeeeeee eee eeeeeeeee eeeee eee MM eeeeeeeeee eeeeeee. Meeee eee eeeeeeee (88eee eee eeeeeee), eee eeeeeeeee eee eeeeee ee ee, eeeeeeeeeeeee, eee eeeeeee eeee M8, eee eee eeeeeee eee eeeeeee. Meeeeeee ee eee eeeeee eeeeeee eee eeeeeee eee ee MM eeeee e MM-MMMM eeeeeeeee eeeeee. Me eeeeeee eee eeeeeee, eee eeeeeee eee eeeeeeeeee, eee eeeeeee eee eeeeeeeee ee eeeeeee, eee eee eeee eee eeeeeeee ee eeeeee eee eeeeeeeeeee. Meee eee eeeeeeee, eee eeeeeee eee eeeeeeee ee eeeeeeeeee eeee ee MeMMM8 eeeeeeee ee eeeeeeeeeeeee, ee-eeeeeeeeee eeeee MM8Me8, eee eeeeeeeeeeeee. Mee eeeeeeee ee eee eeeeeeee eee eeeeeeeee ee MM eee MMM. Mee eeeeeeeeee eee 88% eee eee eeeeeeeeeee eee 8-eeeeeeeeeeeeeee eeee eee 88.8%; eeeee: 88%.

8-(8-Meeeeeeeeeeeee)eeeeeeeee Meee (Meeeeeeee, 88):[‌888‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee, eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

8-(8-Meeeeeeeeee)-8-eeeeeeeeeeeeeee (88.8e, 88.8eeee), 88% ee MMe (88e), MeMe8 (8.8ee, 8.8888eeee), eeeeeeeeeeeeeeeeeeeeeeeeeee (88.8ee, 8.888eeee), eee 8,8-eeeeeee (88eM) eeee eeeeeee eeee e 888-eM Meeeeeeee M eeeeeeeee. Mee eeeeeeeee eee eeeeee eeeee eeeee eeee MM (88eee). Mee eeeeeeeee eee eeee eeeeeeeeeee ee 88eee ee MM eee eee eeeeeee eee eeeeee ee 888888°M eee 8e, eeeeeeeeeee eee eeeeeeee ee 8888eee. MM eeeeeeee eeeeee eeeeeeee eeeeeeeeee; 88% eeeee ee eeeeeeeee eee ee 8-(8-eeeeeeeeeeeeee)eeeeeeeee eeee (88) eee eeee 8.8% ee 8-(8-eeeeeeeeeeeeee)eeeeeeeee eeee eee eeeeee.

References


Cookie-Einstellungen