Science of Synthesis

Reissig, H.-U.; Dugovicč, B.; Zimmer, R., Science of Synthesis, (2010) 41, 308.

gem-Halonitroso intermediates such as ‌241‌ are involved in well-established three-step transformations of oximes ‌240‌ into nitroalkanes.[‌344‌,‌351‌,‌354‌,‌357‌,‌358‌,‌360‌,‌366‌,‌399‌,‌401‌–‌404‌,‌408‌,‌409‌,‌423‌,‌501‌–‌507‌] The oximes ‌240‌ are first oxidized in two steps in a one-pot arrangement into gem-halonitro compounds ‌242‌. Subsequently, the halogen of intermediates ‌242‌ is reductively removed to afford nitroalkanes ‌243‌ (‌Scheme 73‌). Two distinct strategies have been developed to accomplish the conversion of oximes into the corresponding gem-halonitro compounds. The first one utilizes a halogenating reagent such as elemental chlorine,[‌351‌,‌358‌,‌360‌,‌450‌,‌451‌] bromine,[‌344‌,‌357‌,‌399‌,‌401‌–‌404‌,‌423‌] or N-bromosuccinimide[‌408‌,‌409‌] to generate the gem-halonitroso intermediate and then applies an additional oxidant such as ozone,[‌351‌,‌357‌,‌399‌,‌501‌,‌502‌] nitric acid,[‌409‌,‌423‌] trifluoroacetic anhydride/hydrogen peroxide,[‌344‌,‌401‌–‌403‌] nitric acid/hydrogen peroxide,[‌408‌] hydrogen peroxide,[‌404‌] or sodium hypochlorite/tetrabutylammonium hydrogen sulfate[‌354‌,‌358‌,‌360‌,‌399‌] to effect the nitroso to nitro transformation.

‌Meeeee 88‌ Meeeeeee Meeeeeee eee eee Meeeeeeee ee Meeeeeeeeeee eeee Meeeee[‌888‌,‌888‌,‌888‌]

‌Meeeeeeeeee 88‌

M8,M8	Meeeeeeeeeee Meeeeeeeee	Meeeeeeee Meeeeeeeee	Meeeeeeee Meeeeeeeee	Meeee (%)e	Mee
(MM8)8	Me8, MM8Me8, 8–8°M	M8, MM8Me8, 8–8°M	M8, Me/M, MeMM, M8M, ee	88	[‌888‌]
	MMM, MeMMM8, M8M/eeeeeee, 88°M	MMM8, M8M/eeeeeee, ee	MeMM8, M8M/MeMM, ee	88	[‌888‌]
	Me8, MM8Me8, 8–8°M	M8, MM8Me8, 8–8°M	Me, MM8MM•MMe, MMM/M8M, 88°M	88e	[‌888‌]

e Meeee eeee eeeee ‌888‌.

e Meeeeee ee 8,8-eee- eee 8,8-eeeee-eeeeeeeeeeeee.

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

‌Meeeee 88‌ Meeeeeee Meeeeeeee ee eee-Meeeeeeeeeeeeeee Meeee Meeeeeeeeee Meeeeeee Meeeeeeeeee[‌888‌]

Meeeeeeeeeeee, eeeeee eeeeeeee ee eeeeeeeee eeeeeee eeeeeeeee ee eee eeeee eeeeeee ee eeeeeeeeeee eeee Meeee eeee eeee eeeeee ee ee eeeeeeeee eee eee eeeeeeeeeeeeee ee eeeeee eeee eee-eeeeeeeeeeeeeeee.[‌888‌,‌888‌] Mee eeeeeeeeeeee–eeeeeeeee eeeeeeee ee eeeeee eeee ee ‌888‌ ee eeeeeeeeeeeeeeeeee, eeeeee eeeeeeeeeeee ‌888‌ ee eeeee eee eeeee eeeee eeeeeeee ee eeeee eeeeeeee. Me eeeeeeee, eee eeeeeeeeeee–eeeeeeeee ee eeeee ‌888‌ eeeee eeee e 8:8 eeeeeee ee eeeeeeeeeeeee (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeee Mee-Meee Meeeeeeeeeee–Meeeeeeee Meeeeeeee Meeee Meeee[‌888‌]

Meeeee, e.e. ‌888‌, eee eeeeeeeee eeee eee eeeeeeeeeeeee eee-eeeeeeeeeee eeeeeeee, e.e. ‌888‌, ee eee eeeeeeee ee eeeeeeeeeeeeeeee, eeeeeeeee eeeeeee ee eeeeeeee, eee eeeeeeee eeeeeeee (‌Meeeee 88‌).[‌888‌] Mee eeeeeeee ee eeeeeeeeeee ee eeeeeeeee ee eee eeeeeeeeeeeee eeeeeee. Mee eeee ee eeeeeeeeeeeeeeeeee ee eeee eeeeeeee eeeeeeee eeee eee eeeeee eeeeeeeeeee ee eee eeeeee eee ee eeeeeee. Meeeee eeeeeeeeeeee eeeeeeeee, eeeeeeeee eeeeeeeeeeeeeee eeeeeee eeeeeee eee eeeeeeeeeeee ee eeeeeeeeeeeee eeeeeeeeeeeee, eeeeeeeeee eeee eee eeee ee eeeeeeeee ee eee-eeeeeeeeeee eeeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeeeeee ee eeee eeeeee eeee eee eeeeeeeeeeee ee eeeeee.

‌Meeeee 88‌ Meeeee-Meeeeeeee Meeeeeeee ee e eee-Meeeeeeee Meeeeeee[‌888‌]

Meeeeeeeeeeeee eee eeeeeeeeee ee eeeeeeeeeeee ee e eeeeeee ee eeeeeeee ‌888‌–‌888‌ eeee eeeeee eeee ee eee eeeeeeeee eeeee ee eeeeeeee ee eee ee eee eeeee eeeeeeee, eeee eeeeeee eeeeeeeeee ‌888‌ eeeee e eeeeeeeeeee eeeeeeeee. Mee eeeeeeeeeeee eeeeeeee ‌888‌ eee eee eeeeeee eeeeeeeeee ‌888‌ eee eeee eeeeeeeeeeeeee eeeeeeeee eeee eee eeeee eeeeeee ‌888‌ eee eeee-eeeee eeeeeeeeeeeee eeeeeeeee ee eeeeeeeee eeeeeee,[‌888‌] ee eeeeeeeeeeeee eee eeeeeeeeeee eeeeeeeeee eeeeeeeee eeeeeeeee eeee eeeeeeee eeeeeeee (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeee-Meeeeeeee Meeeeeeee ee Meeeeeeeeeee eee Meeeeee Meeeeeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeeeeeeee [‌888‌, M8,M8 = (MM8)8]; Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeeee ee e eeeeee eeeee eee. Meeee eeeeeeeeee ee eeee eeeeeee.

MMMMMMM: Meeee eeeeeeeee eeeeee eeeeeeeee eee eee eeeee eee ee eeeeee eeeeeeeee ee e eeeeee ee eeeee.

Me e eeee ee eeeeeeeeeeeeee eeeee [‌888‌, M8,M8 = (MM8)8; 8.8 e, 8.88 eee] ee MM8Me8 (88 eM) eeeeee ee 8–8°M eeee ee eee eeee eee eeeee e eeee eeeeee ee Me8(e) eeeee eee eeeeeeeee eeee eeee eeee ee e eeeeeeee eeeeeeee eeee. Meee eeee eee eeee eeeeeee eeee e eeeeee ee M8 eee eeeeeeeeeeeee 88 eee ee eeeeee eee eeeeee ee Me8 eee eeee eeeeeee eeee ee M8/M8 eeeeee eeeee eee eeee eeeee eee eeeeeeeeee eeeeeeeeee. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeeee 8-eeeeee-8-eeeeeeeeeeeeeeeee [‌888‌, M8,M8 = (MM8)8] ee e eeeeeee; eeeee: 8.88 e (eeeee).

Meee eeeeeee eee eeeee ee e eeee ee MeMM (8.8 e, 8.888 eee) ee M8M (88 eM) ee e eeeeeeeeeeeee eeeeee. Me eeee eee eeeee 8% Me/M eeeeeeee (8.8 e) eee eee eeeeeeeee eeeeeee eee eeeeeeeeeeee ee e Meee eeeeeeeeeeeee eeeeeeeee eeee ee eeeeeee eeeeeeee ee 888 eMe eeeee eeeeee ee M8 eeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eee eeeeeeee eee eeee eeeeee ee 8°M eee eeeeeeeee ee eeee eeeeeeeeeee eeee MM8MM•MMe (88 e, 8.88 eee). Mee eeeeeee eee eeeeeee ee eeee eeeeeeeee, eeeeeeeee eeee MeMe, eee eeeeeeeee eeee Me8M (8×88 eM). Mee eeeeeeee eeeeeeee eeee eeeee (Me8MM8), eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeeee ee eeee ‌888‌; eeeee: 8.8 e (88%); ee 88–88°M.

References