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.
27.21.1.4 Method 4: Diazo Compounds by Oxidation of Hydrazones

DOI: 10.1055/sos-SD-027-00752

Heydt, H.Science of Synthesis, (200427858.

Dehydrogenation of hydrazones 35 is one of the oldest[‌175‌] and most frequently used methods for the synthesis of diazo compounds 36 (Scheme 16). For a long time mercury(II) oxide was used almost exclusively as the oxidation reagent, but since the 1960s various new oxidation reagents have been found to be efficient alternatives. Silver oxide, manganese(IV) oxide,[‌176‌] and lead(IV) acetate[‌177‌] are often employed as dehydrogenating reagents. In some cases mercury(II) trifluoroacetate, and acetamide, bis(acetylacetonato)copper(II),[‌178‌] nickel peroxide,[‌179‌] triphenylbismuth carbonate, iodine, hydrogen peroxide, oxygen, oxygen in the presence of a cobalt Schiff base complex catalyst,[‌180‌] hypochlorite, hypervalent organoiodo compounds,[‌181‌] and even N,N-bis(trifluoromethyl)aminoxyl radical have been used.

Meeeee 88 Meeee Meeeeeeee ee Meeeeeeeeeeeeee ee Meeeeeeeee[‌888‌‌888‌]

Mee eeeeeeee eeeeeee ee eeee eeeeee eee eeeeeeeeee eee eeeeeeeee ee eeeeee 88 ee eeee eeeeeeee (Meeeee 88)[‌888‌,‌888‌] eee eee eeeeeeeee ee eee eeeeeee eeeeeeeee eeeeeeee eeeeeeee eeee e eeeeeeee eeeeeeee eee eeeeeeeee, eeeeeeeeee eeee eee eeeeeeeee eeeeeeeeee ee eee eeeeeeee eeeeeeee ee ee- ee eeeeeeeeee ee eeeeeeee. Me eeeeeeee eee eeeeeeeeeee eee eeee eeeeeee eeeee eee eeeeeeee eeeeeeee ee eeee eeeeeeee eeee eee eeeeee, e.e. eeeeeee[‌888‌,‌888‌] ee eeeeeeee.[‌888‌] Me eeeeeee eeeeee ee eeeee eeee eeeeeee ee ee eeeeeeeee e eeeeeeeee eeeeee eee eeeee eee eeeeeeeee α-eeeee eeeeee eeee eeeeeeeee eeeeee eeeeeeeeee (Meeeee 88).[‌888‌,‌888‌]

Meeeee 88 Meeee Meeeeeeee ee Meeeeeeeeeeeeee ee Meeeeeeeee[‌888‌,‌888‌]

Meeeee 88 Meeeeeeee ee 8,8-Meeee Meeeeeeeee[‌888‌,‌888‌]

α-Mee(eeeee) eeeeeeeee eeeeee eeee α-eeeeeeeeeeeee eeeeeeeee eeeeeeee ee eeee eeeeeee. Meee eeeeeeee eee eeee eeeeeeee ee eee eeeeeeeee ee eeeeeeeeeeeee[‌888‌,‌888‌] eee eeeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeeeeee, e.e. eee eeeeeeeee ee eeeeeeeeeee 88 ee eee eeeeeeeee ee α-eeeeeeeeeeeee 88 eee eee α-eee(eeeee) eeeeeeeee 88 (Meeeee 88).[‌888‌]

Meeeee 88 Meeeeeeeeeee ee Meeeeeeee ee 8,8-Mee(eeeeeeeeee)[‌888‌]

Mee eeeeeeeee ee 8-eeeee-8,8-eeeeeeeeeeeeee-8(8M)-eee (88) eeee eeeeeeeeee eeeeeeeeeeeeee eeeeee 8-eeeee-8,8-eeeeeeeeeeeeeeee (88) ee 88% eeeee (Meeeee 88). Me ee eeeeeee eeee eee M-eeeeeee eeeeeeeeeeee eeeeeeee 88 ee e eeeeeeeee eeeeeeeeeeee eeee eeeeeeeee eee eeeee eeeeeeee 88 ee eeeeeeeee ee eeeeee eeeeeeee.[‌888‌]

Meeeee 88 8-Meeee-8,8-eeeeeeeeeeeeeeee ee Meeeeeeee ee e 8-Meeeeeeeeeeeee[‌888‌]

Mee eeeeeeeeee ee eeeeeeee eeeeeeeee eee eeee eeeeee eeeeeee eee eeeeeeee ee e eeeeeeeee eeeeeee ee e eeeeee(MM)/eeeeee(M) eeeeeeee ee eee eeeeee eeeeeeeee ee eeee eeeee eeeeeeeee 88 (Meeeee 88). Meeee eeeeeeeee 88 eeee eeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeeeeeeeeeeee ee eeee ee eee eeeeeee eeeeeeee eeeeeeeeeeeeeeeeeeee 88 eee eee eeee eeeeeeee eeeeee 88.[‌888‌] Mee eeeeee eeeeeeee eeeeeeee ee eeeee e eeeeeeeee eeeeeeeeee eeeeeeee eee eee eeeeeeeeeee ee eeeeeeee ee eeeeeeeeee eeeeeee eeeeeee-eeeeeeeeee eeeeeee.[‌888‌]

Meeeee 88 Meeeeeeeeeeeeeeeeee ee eee Meeeeeeee ee Meeeeeeeeeeeee eeee Meeeee Meeeeeee[‌888‌]

Meeeeeeeeee 88

Me8 M8 Meeeee 88 Meeee 88 Mee
Meeee (M/M) Meeee (%) Meeee (%)
8-MeM8M8 M 8.8:8 88 88 [‌888‌]
8-MeM8M8 Me 8.8:8 88 [‌888‌]

Meeeeeeee eeee eeeeee eeeeeeeeee eeeee eeeeeeeee, e.e. 8-eeeeeeeeeeeeeeee, eee eeeeeeeeeee eeeeeeee ee eeee(MM) eeeeeee, eee eeee eeeeeeeeee eeeee eeeeeeeee eee eee eeeeeeeeee ee eeee eeeeee eeeeeee ee eeeee eeeee eeeeeeeeeeeee ee eeeeee eeee eee eeee(MM) eeeeeee. Me e eee eeeeeeee, eeeeee eeeeeeeee eeeee eeeeeeeee eee ee eeeeeeeeeee eeeeeeeeeee eee eeeeee ee eeeeeeeee ee eeeeeeeeee ee 88°M ee e eeeee eeeeeeeeeee eeee eeee(MM) eeeeeee ee eeeeeeeeeeeee/eeeeeeeeee, 8-eeeeeeeeeeeeeeee/eeeeeeeeeeeeeeeee, eeeeeeeeeeeeeeeeeeee/eeeeeeeeeeeeeeeee, ee eeeeeeeeeeeeeeeeeeee/eeeeeeeeeeeeeee.[‌888‌]

Meeeeeee ee eeeee eeeeeeeee eeeeee ee eee eeeeeeeee ee eeeeeeeeee eee eeeee ee Meeee 8.

Meeee 8 Meeee Meeeeeeee ee Meeeeeeee ee Meeeeeeeee[‌888‌‌888‌,‌888‌,‌888‌‌888‌]

Meeeeeeee Meeeeeeee Meeeeee Meeeeeee Meeeeeeeee Meeee Meeeeeee Meeee (%) Mee
MeM Me8M 8888 [‌888‌]
MeM8 MMMe8 88888 [‌888‌,‌888‌]
Me(MMe)8 MeMM 8888 [‌888‌]
Me(eeee)8, M8 Me8Me, 88°M 88 [‌888‌]
[MeM(ee)8]8+ 8MMe MM8Me8, ee 888 [‌888‌]
MeM8 MMMe8, ee 88 [‌888‌]
MeM eeeeeeeee eeeee 8888 [‌888‌,‌888‌]
Me8M8 Me8M, ee
88
[‌888‌]
MeM Me8M 888 [‌888‌,‌888‌]
Me8M Me8M 88 [‌888‌]
M8, Me(eeeee) 8-eeeeee-8M-eeeeeeeee, MeMM 88e [‌888‌]
MeM8 Me8M, MeMM8, ee e [‌888‌]
MeM Me8M, MeMM, MMM 8888 [‌888‌‌888‌]
Me(MMe)8 MMMe, MMM 88 [‌888‌]

e Me MM8Me8 ee eeeeeee eeeee eeeeeeeee ee eeeeeeee.

e 8-(8-Meeeeeeeeee)eeeeeeee (88%) eee eeee eeeeeeee.

e Mee eeeeeeeeeee ee eeeeeeee eee eeee ee eeee ee eeee ee eeeeeeee.

e MMM=eeeeeeeeeeeeeeeeeeee.

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeeee:[‌888‌]

MMMMMMM: Meeeeeeee ee eeeeeeeee eee eee eeeeeeee eeee eeeeeeee ee eeeeeee. Me ee e eeeeee eeee eee eeeeee eeeeeeee eeeeeeee eee e eeeeeeee eeeee eeeeeeeeee.

Meeeeeee (8.88e, 88.8eeee) eee eeeee ee eeeeeee eeeee 88% eeeeeeeee (88.8e, 888eeee) ee 88°M eee eeeeeee eee ee eeeeeeeeee 88eee ee eee eeee eeeeeeeeeee. Meeee eeeeeee ee ee, MM8Me8, eee eeeee eee eee eeee eee eeeeee eeee eee. MeMe (8×88eM), eeeee (M8MM8), eee eeeeeee ee eeeee ee e eeeeee ee eeeee 8888eM. MMM (88eM) eee eeeee eee eee eeeeeeeee MM8Me8 eee eeeeeee ee eeeee.

Mee eeee ee eeeeeeee eeeeeeeee ee MMM eee eeeeee ee 88°M, eee eeeeeeeeeeee eeeeeeeeeeeeeeeeeeee (88eM) eee Me(MMe)8 eeee eeeee. Mee eeeeeee eee eeeeeee eee 88eee ee 88°M, eeeeeee eeee eeee eeeeee (8×888eM) eee eeeeeeeee eeeee eeeeeeeee eeeeeeeeee. Mee eeeeeeee eeeeee eeeeeeee eeee eeeeee eeee eeee (88°M) 88% MMM (8×88eM), eeeee eeeeee ee eee eee eeee eeeee, eee eee eeee eee eeee eeeeeeee. 8-Meeeeeeeeeee ee eeeeee ee eeeeee eee eeeeeee eeee. Me eeeeeee ee eee eeeeee eeeeeeee eee eeeeeeee eeee e M8MM8 eeee; eee M8 eeeeeee eeeeeeeeeee ee e 88% eeeee ee eee eeeee eeeeeeee.

References