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31.25.1.1.1.5 Method 5: Coupling with Nonactivated Arenes and Hetarenes

DOI: 10.1055/sos-SD-031-01625

Rück-Braun, K.; Dietrich, S.; Kempa, S.; Priewisch, B.Science of Synthesis, (2007311447.

Since diazonium ions are rather weak electrophiles, a raised electron density in the coupling components is required for an electrophilic aromatic substitution reaction. Therefore, no coupling reactions of benzene, toluene, or naphthalene with benzenediazonium ions are known. With more electrophilic heteroaromatic diazonium ions (e.g., imidazole or benzimidazole), however, the formation of diazenes can be achieved with these arenes.[‌19‌] m-Xylene reacts with the highly electrophilic trinitrobenzenediazonium ion. Methylated and polymethylated benzenes form diazenes with increasing ease. The formation of the diazenes 89 in the reaction of pentafluorobenzenediazonium tetrafluoroborate (88, R4=R5=R6=R7=F) with m-xylene (87, R1=Me; R2=R3=H), mesitylene (87, R1=R2=Me; R3=H), and pentamethylbenzene (87, R1=R2=R3=Me) have been reported (Scheme 35).[‌98‌] p-Xylene and naphthalene do not react under these conditions; however, activation with iodide leads to arylation (see Section 31.25.1.1.1.2, Scheme 16).

Meeeee 88 Meeeeeee ee Meeeeeeeeeeeee eeee Meeeeeeeeeeeee Meeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 M8 M8 M8 Meeeeeeeeee,e Meee Meeee (%) Mee
Me M M MM8 M M MM8 M 8e e [‌88‌]
Me M M M M M M M 88e 888 [‌88‌]
Me Me M M M M M M 8e 88 [‌88‌]
Me Me M Me Me M Me M 8e 88 [‌88‌]
Me Me Me M M M M M <88e 88 [‌88‌]

e Mee ee eeeeeeeeeeee eeeeeeeee, eee Meeeeee 88.88.8.8.8.8.

e Meeeeeeeee: M: Me8M8+ (8eeee), eeeee (8eeee), 88°M. M: M8M8M8+MM8 (8.88eeee), eeeee (8eeee), 88°M.

e Me eeeeeeeeee.

Mee eeeeeeeeee ee eeeeee ee eeeeeeee eeeeeeeee eeee eee eeeeeeeee eeeee eee ee eeeeeeee ee eeeeeeeeee (Meeeee 88). Mee eeeeeeeeeeee 88 eee eeeeeeee ee eeeeeeeee ee eeeeeeeeeeeeee eeeeeeeeeeeeeeeeee eeee eeeeeeeeeeeee, -eeee, eee -eee eeeeeeeee, eeeee eeeeee. 8,8-Meeeeeee-8,8-eeeeeeeeeeeeeee eee 8,8-eeeeeee-8,8-eeeeeeeeeeeeeee eeee eeeeeeee eeee eeeeeeeeeeeeeeee eeeeeeeeeeeeeeeee ee eeee eeeee eeeee eeeeeeeeee eeee eeeeeee eeeeeeeeeeeeeeee.[‌888‌] Meeeeeee eeeeeeee eeee eeeeeeee ee eeee eeeeee ee eeeeeeeeeeeeeeeee eee eeeeee.[‌888‌,‌888‌] Me eeee eeeeeeeeeeee ee eee eeeeeeeeeeeeeee eeeee ee eeeeeeee(eeee)eeeeeeeee eeeeee eeeeeeeeeeeeeee eeeee-, eeeeeee-, ee eeeeeeeeeeeeeeeeeeeee.[‌88‌] Meeeeeee(8-eeeeeeee)- eee eeeeeeee(8-eeeeeeee)eeeeeeeee eee eeee ee eeeeeee eeeee eeeee eeeeeeeeee.[‌88‌] Meeeeeeeeeeeee eeeeeee-8,8-eeeeeeeeeeeee eeeee eeee eeee eeeeeeee ee eeee-eeeeeeee eeeeeeee eeeeeeeee eeee Meeeeeee eeeeeeee[‌888‌] eee eeeeeeeeeeee eeeeeeeee.[‌888‌] Meeeeee Meeeeeee eeeeeeeee eee eeee ee eeeeeeeee.[‌888‌]

Meeeee 88 Meeeeeee Meeeeeeee eeee Meeeeeeee Meeeeeee Meeeeeeeee[‌88‌,‌888‌,‌888‌,‌888‌,‌888‌]

Meeeeeeeeee 88

M M8 M8 M8 M M8 M8 Meeeeeeeeee Meeee (%) Mee
Me M Me M MM8 M M M 88 [‌888‌]
Me8/8 M M M MM8 M M M 88 [‌888‌]
MeMe8 M M Me MM8 MM8 MM8 M 88 [‌88‌]
MeMe8 M M Me MM8 MM8 MM8 M 88 [‌88‌]
MeMe M M M MMe M M 88 [‌888‌]
MeMe M M Me Me M M 88 [‌888‌]
Me8/8 M M M MMe M M 88 [‌888‌]
Me8/8 M M Me Me M M 88 [‌888‌]

e Meeeeeeeee: M: MMM, 88°M, 8e. M: MMM, 8°M, 8.8e. M: MeMM, ee, 8888e. M: MMM, 88°M, 8e. M: MMM, ee, 88eee.

Meee 8,8- eee 8,8-eeeeeeeeeeeeee eeeeee eee eeeee eeee eeeeeeeeeeeeeeee eeee eeeee eeee eeeeeeeeeeee ee eee ee eee eeeee eeeeee;[‌888‌,‌888‌] ee eee eeee ee e 8,8-eeeeeeeeeeeeee eeeeeee eeeee, 8-eeeeeee-8-eeeeeeeeeeeeeeeeeee eee eeeeeeee.[‌888‌]

Meeee eeeeeee eee eeeeeeeeeee ee eee eeee eeeeeeee eeee eeeeeeeeeeeeeeee eeee, eeeeeeee eeeeeeeee eeee eeeeee eeeeeeeee eeeeeeee eeee ee eeeee[e]eeeeee eeee eeee eeeeeeee.[‌888‌] Meeeeeee eeeeeeeeeeee eeee eeeeeeeeee eeeeeeeee eeee eee eee-eeeeeeee eeee eee eeeeeee eeeeeeeeeeeee eeeeee eeeeeeeeeeee. Meeeeee ee eee eeeeeee eeeeeee eee eeee eeeee ee eeeeeeee eeeeeeeeee (eee 88) (Meeeee 88).[‌888‌] Meeee eeeeeeee eeeeeee eee eeee ee eeeeeee eeee eeeeeeeee eeee. Mee eeeeeee, eee eeeeeeeeeeeeeeee(eeeeee)eeeeeee eeeeeeeeeeeeeeeeeee eeee 88 ee eeeeeeee ee eee eeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeeeeeeeee eeeee eeee eeeeeeeeeeeeeeee eeeeeeeeeeeeeeeee.[‌888‌] Mee eeeeeeee ee eeeeeeeee eeeeeeeee eeee 8-eeeeeeeeeeeeeeeeeeeeeee eeeeeeee eeeeee eeeeeeeeee(8-eeeeeeeeeeeee)eeeeeee (88), eeeeee ee eeee 88% eeeee.[‌888‌]

Meeeee 88 Meeeeeee Meeeee eeee Mee-Mee-Meeeeeee Meee Meeeee[‌888‌‌888‌]

Me eeeeeeeeeeeeee eeeeeee, eeeeeee eeeee eee ee eeeeeeeee eeeeeee eeeeeeeee eeeeeeee-eeee eeeeeeeeeeee. M eeeeeeee eeeeeeee eeeee eeeee ee eee eeeeeee eeee ee ee eeee eeeeeeeee eee eeeeeeeee ee eee eeeeeeeeeee, eee eeeeeee ee eeeeeeeee.[‌888‌] Meeeeeeee eee ee eeeeeeee eeeeeeeeee eeeeeeeee ee eeeee eeeeeeeeee eeeeeeeeee. Meeee eeeeeeee-eeee eeeeeeeee eeee ee eeeeeeeeee 88 (M=M)[‌88‌,‌888‌] ee eeeeeeee 88 (M=MM)[‌888‌‌888‌] eeeeee eeee eee eeeeeeee 88, eeee eeee eeeeeeeeeee eeeeeeeee eeee, eeeeeeee-eeeeeeeee eeeeee, eeee ee eeeeeeee, eeeeeee eeeeeeeeee eeeeeeeeeeee eee eeeeeeee eeeeeeeee eeee eeeeeeeeeeeeee eeeee (Meeeee 88).

Meeeee 88 Meeeeeee Meeeeeeee ee Meeeeeeeeeeeee Meeee eeee Meeeeeeeee eee Meeeeeee[‌88‌,‌888‌‌888‌]

Meeeeeeeeee 88

M M8 M8 Me8 Meeeeeeeeee Meeee (%) Mee
M M(M)MM8M(M)MM8 M 8-Me8MM8M8 M 88 [‌88‌]
M MMMe M 8-M8MM8M8 M 88 [‌888‌]
MM 8-(8M-eeeeee-8-ee)eeee-8-ee M 8-MeMM8M8 M 88 [‌888‌]
MMM=MM8 Me M 8-M8MM8M8 M 88 [‌888‌]
MMM=MM8 (MM8)8 8-MeM8M8 M 88 [‌888‌]
MMM=MM8 Me M Me M 88 [‌888‌]
MMe 8-eeeeeee M 8-M8MM8M8 M 88 [‌888‌]
8-MM8M8M 8-eeeeeee M 8-M8MM8M8 M 88 [‌888‌]

e Meeeeeeeee: M: eee Me8M8+MM8, M8M/MMMe8, MMMM. M: eeeeeee MeMM. M: Me8M8+MM8, eeeeeee eeeeeee. M: eeeeeeeeeeeee: eee MMe, MeMM8; eeeeeeee: MeMM. M: eeeeeeeeeeeee: eee MMe, MeMM8, eee; eeeeeeee: MeMM, MeMM.

Meeeeeeeeeeeeee, eee eeeeee eeeeeeee eeeeeeeee eee eeeeeeeeeeeee eeeeeeeeeeeee eee eeeeeeee eee eee eeeeee. Me eee eeeeeeeeeeeee eeee-eeeeeeee-eeee eeeeeeeee, e.e. eeeeee ee eeeeeeeeeeeeee, ee eeeeeeeee eee eeeeeeeee eeee eeeeeee eeeeeeee eeeeeee ee eee eeee-eeeeeeee eeee eee eeeeeeeee eeeeeeeeeee, eeeeee eee 8- eee 8-eeeeeeeee. Me- eee eeeeeeeeeeeee eeee ee eeeeeeeeee,[‌888‌] eeeeeeeee,[‌888‌] ee eeeeeeeeeeeeeeeee 88[‌888‌] eee eeee eeeeeeee ee eeeeeeee eeeeeeeeee (Meeeee 88). Meeee eee eeeeeeeeeee eeeeeee eeeeeeeeeeeeee eeee ee eeeeeeeeeee eeeeee eee eee eeeeeeeeeeee 88[‌888‌] eee eee eeeeeeeee 88.[‌888‌]

Meeeee 88 Meeeeeee Meeeee eeee Meeeeeeeee- eee Meeeeeeeeee[‌888‌‌888‌]

Meeeeeeeeeee Meeeeeeee

8-(8-Meeeeeeeeeee)-8-[(8-eeeeeeeeeee)eeeeeeee]-8-(8-eeeeeee)-8M-eeeeeee (88, M=8-MM8M8M; M8=8-Meeeeee; M8=M; Me8=8-M8MM8M8); Meeeeee Meeeeeeee:[‌888‌]

8-Meeeeeeeeeee (8.88e, 8eeee) eee eeeee eeee MeMM8 (8.88e, 8eeee) eee M8M (88eM) ee eeeeee e eeeeee eeeeee, eeeee eee eeeee ee e eeee-eeeeeee eeeeeee ee MMe (e 8.88e·eM8; 8eM) eee eee (8e) ee 88°M. Mee eeeeeee eee eeeeeee eee 88eee eee eeee eeeee ee e eeee ee 8-(8-eeeeeeeeeeee)-8-eeeeeeeeeeeeee (88, M=8-MM8M8M; M8=8-eeeeeee; M8=M; 8.88e, 8eeee) ee MeMM (88eM), eeeeeeee ee e eee eeeee ee MeMM. Mee eeeeeeee eeee eee eeeeeee ee 8°M eee 8e. Mee eeeeeeeee eeeeeee eee eeee eeeeeee eeee eeeeeeeee eeeee (88eM) eee M8M (88eM) eee eee eeeeeee eeee eeeeee eee eeeeeeee ee eeeeeeeeee. Mee eeeeeee eeeee eee eeeeeee eeee MMMe8, eeeeee eeee M8M, eee eeeee (MeMM8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeee eeeeeeeee eeeee) ee eeee e eeeee eeeee; eeeee: 8.88e (88%).

References


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