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Please login to access the full content or check if you have access via Method 1: Condensation of Nitrosoarenes with Arylamines in Acetic Acid

DOI: 10.1055/sos-SD-031-01625

Rück-Braun, K.; Dietrich, S.; Kempa, S.; Priewisch, B.Science of Synthesis, (2007311457.

The condensation of aromatic nitroso compounds with aromatic amines in acetic acid, furnishing diaryldiazenes 114, has been known for more than 100 years (Scheme 49). Although first discovered by Baeyer in 1874,[‌203‌] the reaction is often referred to as Mills coupling.[‌204‌] The attack of the amine at the nitroso group is the rate-determining step in the acidic medium.[‌205‌] Electron-withdrawing substituents in the nitroso compound increase the reaction rate, while electron-releasing substituents decrease it. For substituents on the amine, the effect is reversed.[‌206‌] Many functional groups are tolerated under these conditions, and a broad range of unsymmetrically substituted diaryldiazenes can be prepared in good to excellent yields. In many cases the diazene begins to separate as a solid during the course of the reaction, or it can be precipitated by addition of water to the reaction mixture. Alternatively, the product may be isolated by evaporation of the solvent or by extraction using pentane, chloroform, diethyl ether, or ethyl acetate.[‌207‌‌214‌]

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Meeeeeeeeee 88

Me8 Me8 Meeee (Me8MM/Me8MM8) Meeeeeeeee Meeee (%) Mee
8-e-MeM8MM8M8 8-MM8M8 8.8:8 ee, 88e 88 [‌888‌]
8-MeM8M8 8-M8M8M8 8:8 <88°M, 888e 88 [‌888‌]
8-[(MM)8M=MM]M8M8 8-MeMM8M8 8.8:8 ee, 888e 88 [‌888‌]
Me 8.8:8 ee, 8e 88 [‌888‌]
8-MeM8M8 Me 8:8 ee, 88e 88 [‌888‌]
8-(e-MeM8MMM8)M8M8 8-(MeeeMMMM8)M8M8 8:8 ee, 88e 8888 [‌888‌]
8-M8MM8M8 8-MeM8M8 8.8:8 ee, 88e 88 [‌888‌]
Me 8.8:8 ee, 88e 88 [‌888‌]

Meeeeeeeeeee eee eeeee eeee eee eeeeeeeee ee eee eeeeeee eeeeeeee. Me eeee eeeeeee, eee eeeeeeeeeee ee eeeeeeeeeeeee 888 ee eeeeeeeee ee eeeeeeeeee ee ee eeeeeee eeeee, eeeee eeeeeeeeeeee ee eee eeeee eee eeeee eeeeeeee eeeeeeeeeeeee eee ee eeeeeee (Meeeee 88).[‌888‌,‌888‌] Mee eeeeeeeeee eeeeee ee eee eeeeeeeee eeee, eeeeee eeeeeeeeeeeee eeeeee eee eeeeeeeeeee (eee Meeeeee 88.88.8), ee eee eeeeeeeee ee eee eeeeeeee eeeeeeee ee eeee eee eeeeeeeeeeeeee 888 eee eee ee eeeeeeeee eeeeeeeeee.

Meeeee 88 Meeeeeeeeeee ee Meeeeeeeee eeee Meeeeeeeeeeee Meeeeeee ee Meeeeeeee eeee Meeee[‌888‌,‌888‌]

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

Meeeee 88 Meeeeeeeeeee ee Meeeeeeeee eeee Meeeeeeeeeeee ee e Meeeeee ee Meeeeee Meeeee Meee eee ee Meeeeee Meeeeee[‌888‌,‌888‌‌888‌]

Meeeeeeeeee 88

Me8 Me8 Meeee (Me8MM/Me8MM8) Meeeeeeeee Meeee (%) Mee
8-MM8MM8M8 8-(MeeeMMMM8)M8M8 8:8 MMMM/MeMM (8:8), ee, 88e eeeee [‌888‌]
8-Mee 8-MM8M8 8:8 MM8Me8/MeMM (8:8), ee, 88e 88 [‌888‌]
8-MeMM8M8 8.88:8 MeMM/MeMM (88:8), ee, 8e 88 [‌888‌]
8,8-(MeM8M)8M8M8 8-(MMMM8)M8M8 8:8 MM8Me8, MeMM (8 eeeee), ee, 88e 88 [‌888‌]
Me 8-MeM8M8 8:8 MeMM/MeMM (88:8), 88°M, 88e 88 [‌888‌]
8-M8MM8M8 8:8 MeMM/MeMM (88:8), 888°M, 8e 88 [‌888‌]
Me 8:8 MMMe8, MeMM (8 eeeee), ee, 88e 88 [‌888‌]
8-eeeeeee 8-MeM8M8 8.8:8 MM8Me8, MeMM (8 eeeee), ee, 88e 88 [‌888‌]
8-Mee 8:8 MeMM/MeMM (8:8), eeeeee, 88e 88 [‌888‌]

Meeeeeeeeeee Meeeeeeeee:

(8M)-8-[(eeee-Meeeeeeeeeeeee)eeeee]-8-[8-(eeeeeeeeeeeeee)eeeeee]eeeeeeeee Meee (888, Me8=Me; Me8=8-{(8M)-8-[(eeee-Meeeeeeeeeeeee)eeeee]-8-eeeeeeeeeeee}eeeeee):[‌888‌]

MMMMMMM: Meeeeeeeeeeeee eee eeeeeeeeeee eeeeeeeeeee eee eeeee eee eeeeeeeeeeee. Meeeee eeeeee eeeeeeeeeee eeeeee ee eeeee eeeeee eeeeeeeee, eeeeeeee, eee eeeeeee.

MeMM (888ee; 8.8eeee) eee eeeee ee e eeee ee (8M)-8-[(eeee-eeeeeeeeeeeeee)eeeee]-8-eeeeeeeeeeeeeee eeee (8.8e, 8.8eeee) ee eeeeeee MeMM (888eM) eee eee eeeeeee eee eeeeeee ee ee eee 8e. Mee. ee MeMMM8 (888eM) eee eeeee eee eee eeeeeee eee eeeeeeeee eeee MeMMe (8×888eM). Mee eeeeeeee eeeeeee eeeee eee eeeee (MeMM8) eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/MeMM 8:8) eeee ee eeeeee eeeee; eeeee: 888ee (88%).

Meeeee 8-[(8-Meeeeeeeeee)eeeeeeee]eeeeeeee (888, Me8=8-MeM8MM8M8; Me8=8-MeM8M8); Meeeeee Meeeeeeee:[‌888‌]

Meeee 8-eeeeeeeeeeee (888ee, 8.88eeee) eee eeeee ee e eeee ee eeeee eeeeee 8-eeeeeeeeeeeeeee (888; Me8=8-MeM8MM8M8; 888ee, 8.88eeee), eeeeeeee ee eeeeeeeee ee eeeeee 8-eeeeeeeeeeeee eeeee Meeee (eee Meeeeee Mee eeeeeee eee eeeeeee ee ee eee 88e (MMM eeeeeeeeee). Mee eeeeeeeeeee eee eeeeeeeee ee eeeeeeeeee, eeeeee eeee M8M, eee eeeee (eeeeeeeeee, Meeeeeee). Meeeeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/eeeeeee 8:8) eeeeeeee ee eeeeee eeeee; eeeee: 888ee (88%); ee 888°M.