Science of Synthesis

Scholz, U.; Schlummer, B., Science of Synthesis, (2007) 31, 1646.

Arylamines can be synthesized by a reaction type in which during the reaction a C—H bond is broken and a new C—C bond is formed; therefore, the C—N bond has to be already present in the starting material. A well-known [5,5]-sigmatropic rearrangement, the benzidine rearrangement of 1,2-diarylhydrazines, is a very good example of this type of reaction. Thus, N,N′-bis(2-bromophenyl)hydrazine rearranges to 3,3′-dibromobiphenyl-4,4′-diamine (‌187‌) in good yield when treated with concentrated hydrochloric acid (‌Scheme 204‌).[‌372‌]

‌Meeeee 888‌ Meeeeeeee ee 8,8′-Meeeeeeeeeeeeee-8,8′-eeeeeee ee Meeeeeeeeeeee ee M,M′-Mee(8-eeeeeeeeeee)eeeeeeeee[‌888‌]

Meee eee ee eee eeee eeeeeeeee ee eee eeee eeeeee ee eeeeeee, eee eeeeeeeee eeeeeeeeeeeee eeeeee eeee eeeee; eeeeeee, e eeeeeeeeeee eeeeeeeeeeeee ee eeeeeeee. Meee eeeeeeee eeee eeeee eeeee ee e eeee eeeeeeee ee eee eeeeeeeee eeeeeeeeeeeee. Me ee eeeeeee, M-(8-eeeeeeeeeeee)-M′-eeeeeeeeeeeeeee eeeeeeeeee ee 8-eeeeeeeeeeeeee-8,8′-eeeeeee (‌888‌) (‌Meeeee 888‌),[‌888‌] eee eeee eeeeeeeeeeeeee ee ee eeeeee eeeeeeeee eeeeeeeeee.

‌Meeeee 888‌ Meeeeeeee ee 8-Meeeeeeeeeeeee-8,8′-eeeeeee ee Meeeeeeeeeeee ee M-(8-Meeeeeeeeeee)-M′-eeeeeeeeeeeeeee[‌888‌]

Me eeee eeee eeeeeeeee eee eeeeeee, ee eeeee-eeeeeeee eeeeeeeeeeeee ee eeeeeeee. Meee eeeeeeee eeee ee eeeeeeee eee eeeeeeee ee e M—M eeee eee eeeeeeeeeee eeee e M—M eeee eee ee eeeee eeee ee Meeeeee ‌88.88.8.88.8‌.

Meeee eeeeeeeeeeeee M,M′-eeeeeeeeeeeeeeee eee eeeeeeeeeeee eeeeeeeeeee eeee eee eeeeeeeeeeeee eeeeeeeeeeeeee eee eeee eeeeeee ee e eeeeeeeee-eeeeeeeee M—M eeeeeeee (eee Meeeeee ‌88.88.88.8.8.8‌), eee eeeeeeeee eeeeeeeeeeeee eee ee eeeeee eeeeeeee eeee eeee eeeeeeee eeee ee eeeeee e eeeeeeeee eeeeeeee ee eeeeeeee-8,8′-eeeeeee eeeeeeeee. Meee ee eeeeeeeeeee ee eee eeeeeeeee ee eeeee 8,8′-eeeeeee-8′-eeeeeeeeeeeeee-8-eeeeeeeeeee (‌888‌) eeee 8-eeeeeeeeeee eee eeeee 8-[8-(eeee-eeeeeeeeeeeeee)eeeeeeeee]eeeeeeee (‌Meeeee 888‌).[‌888‌] Mee eeeeeeeeeee eeeeeeeeeeeee eee ee eeeeeeeeeeee eeeeeeeeee, eeeeeee, eeee ee eeee eeeee eeeeeeee eeeee eeeeee ee eeeee ee eeee eeeeeeeeeee.

‌Meeeee 888‌ Meeeeeeee ee Meeee 8,8′-Meeeeee-8′-eeeeeeeeeeeeee-8-eeeeeeeeeee eeee 8-Meeeeeeeeee eee Meeee 8-[8-(eeee-Meeeeeeeeeeeee)eeeeeeeee]eeeeeeee[‌888‌]

Me eeeeeeeeeee eeeeeeee ee eeeeeeee-8,8′-eeeeeee eeeeeeeee ee eee eeeeeeeeeeeeee eeeeeeeee eeeeeeeeeeee ee eeeee(eeee)eeeeee, eeee ee M,M-eeeeeeeeeeeeeee ee eeeee M,M,M′,M′-eeeeeeeeeeeeeeeeeee-8,8′-eeeeeee (‌888‌) eeee eeeeeee eeee e eeeeee eeeeeeeee eeeee, e.e. eeee(MMM) eeeeeeee[‌888‌] ee eeeeeeeee eeeeeeeeeeee (‌Meeeee 888‌).[‌888‌]

‌Meeeee 888‌ Meeeeeeee ee M,M,M′,M′-Meeeeeeeeeeeeeeeeee-8,8′-eeeeeee ee Meeeeeeee Meeeeeeeeeee ee M,M-Meeeeeeeeeeeeee[‌888‌]

Meeeeeeee eeeeeeeeee eee eeee eeeeeee e eeeeeeeeeeeee eeeeeeee ee eeee M-eeeeeeeee eeeeeeeeee, eeeee ee eeeeeeeee eeeeeeee ee ee eee Meeeeee–Meeeeee eeeeeeeeeeeee.[‌888‌] Meee eeeeeeee eeeee eeeee ee eee eeeeeeee ee eeeeee, eeee, ee eeeeeee eeeeeeeee ee eeee eeeeeeeeeeee; eeeeeeeee, eeeeee-eeeee eeeee eeeeee eee eeeeeee ee eeeeeee eeee eeeeeeeee eeee ee eeeeeeeeeeee eee eeeeeeeeeee. Mee eeeeeeeee eeeeeeeeee ee eeee eeeeeeeeeeeee ee eeee eeeeeee ee M-eeeee-, M-eeeeee-, ee M-eeeeeeeeeeeee. Mee eeeeeee, M-eeeeeeeeeeee eeeeeeeeee ee 8-eeeeeeeeeeee (‌888‌) ee eeee eeeee eeeee eeeeee(MM) eeeeeeee eeee eeeeee eeee ee 888°M (‌Meeeee 888‌).[‌888‌]

‌Meeeee 888‌ Meeeeeeee ee 8-Meeeeeeeeeee ee Meeeeeeeeeeee ee M-Meeeeeeeeeee[‌888‌]

Mee Meeee eeeeeeeeeeeee ee eeeeeeee eeeeeee ee e eeee-eeeee eeeeeeee, eee eee eeeeeee eeeeeee ee eeee eeeeeeee ee eeeeee eeeeeeeee eee eeee eeeeeee eeee eeeeee eee eeeeee. Me ee eeeeeee, eeee M-eeeeee-M-eeeeeeeeeeeeeee ee eeeeee eeee eeeeee eeeee, ee eeee eeeee ee eee eeee eeeeeeee ee eee eeeee ee eeeeeeee; eeeee eeeeeeeeee eeeeee, 8-(8-eeeeeeeeeee)eeeeeeee (‌888‌) eee ee eeeeeeee ee eee eeeee (‌Meeeee 888‌).[‌888‌]

‌Meeeee 888‌ Meeeeeeee ee 8-(8-Meeeeeeeeee)eeeeeeee ee Meeeeeeeeeeee ee M-Meeeee-M-eeeeeeeeeeeeeee eee Meeee-Meee Meeeeeeeeeeee[‌888‌]

Meeeeeeeeeeeeee eeeeeee eee-Meeee-eeee eeeeeeeeeeeeee ee eeeeee ee eeee eeeee eeee eeeeee eeeeee eeee eee eeeeeee eeeeeeee. M eeeeeee, eeeeeeeeee eeeeeeee ee M-(8-eeeee)eeeeeeeee eeeeee (8-eeeee-8-eeeeeeeeeeee)eeeeeeeeeeeeeee (‌888‌) ee eeee eeeee (‌Meeeee 888‌).[‌888‌]

‌Meeeee 888‌ Meeeeeeee ee (8-Meeee-8-eeeeeeeeeeee)eeeeeeeeeeeeeee ee Meeeeeeeeeeee ee M-(8-Meeee)eeeeeeeee eee Mee-Meeee-Meee Meeeeeeeeeeee[‌888‌]

Mee eeeeeeeeeeee ee e eeeeeeeeeeeeee eeeee ee eee 8-eeeeeeee ee eeeeeee eeeeeeeeee eee ee eeeeeeee eeeee eee Meeeeeee–Meeeee eeeeeeeeeeeee. Me eeeeeee ee eeeeeeeee eeee eeeeeeee eeeeeeeee ee eeee eee M-eeee-M,M-eeeeeeeeeeeeeeeee. Mee eeeeeee, M-(8-eeeeeeeeeeee)-M,M-eeeeeeeeeeeeeeeee (‌888‌) ee eeeeeeee ee eeeeeeeee ee 8-eeeeeeeeeeeee eee eeeeeeee eeeeeeeee eeee eeeeeeeeee eeeeeeeee eee eeeeeeeeeeeee. Meee eeeeee eeeeeeee eeeeeeeeeeee eeee eeeeeeeeee ee eeee eeeee ee 8-eeeeee-8-[(eeeeeeeeeeeeee)eeeeee]eeeeeee (‌888‌) ee eeeeeee eeee eeeeeeeeeeeee eee 8 eeeee (‌Meeeee 888‌).[‌888‌]

‌Meeeee 888‌ Meeeeeeee ee 8-Meeeee-8-[(eeeeeeeeeeeeee)eeeeee]eeeeeee eeee M-(8-Meeeeeeeeeee)-M,M-eeeeeeeeeeeeeeeee eee Meeeeeee–Meeeee Meeeeeeeeeeee[‌888‌]

Meeeeee eeeeee [8,8]-eeeeeeeeeee eeeeeeeeeeeee, eee Meeeeee eeeeeeeeeeeee, eee eeee ee eeee eee eee eeeeeeeee ee eeeeeeeeee. Mee eeeeeee, M-eeeee-8,8-eeeeeeeeeeeeeee eeeeeeeeee ee 8-eeeee-8,8-eeeeeeeeeeeeeee (‌888‌) eeee eeeeee eeee eeeeee Meeee eeeee ee eeeeeeee eeeeeeee (‌Meeeee 888‌).[‌888‌] Meeeeee, eeee ee eeeeeeeeeeee eee eeeeeee ee eeee eeeee eeeeeeeee ee eee eeeeeeeee, eee Meeeeee eeeeeeeeeeeee ee eee eeee eeeeeeeee eee eee 8-eeeeeeeee eeeeee ee eee eeee eeeeeee. Meeee ee eeee eee eeeeeeeeeee, eeee eeeeee eee eeeeeee eeeeeeee.[‌888‌]

‌Meeeee 888‌ Meeeeeeee ee 8-Meeee-8,8-eeeeeeeeeeeeeee eeee M-Meeee-8,8-eeeeeeeeeeeeeee eee Meeeeee Meeeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeee 8,8′-Meeeeee-8′-eeeeeeeeeeeeee-8-eeeeeeeeeee (‌888‌):[‌888‌]

Meeee 8-[8-(eeee-eeeeeeeeeeeeee)eeeeeeeee]eeeeeeee (888 ee, 8.88 eeee), 8-eeeeeeeeeee (888 ee, 8.88 eeee), Me(MMe)8 (88 ee, 8.88 eeee), e-Me8M•MMM8 (88 ee, 8.88 eeee), Me8MM8 (888 ee, 8.88 eeee), eee eeeee eeeeeee (8 eM) eeee eeeee ee ee. Mee eeeeeee eee eeeeeee eee 88 eee ee ee eee eeee eeeeeeee eee 8 e. Mee eeeeeeeee eeeeeee eee eeeeeeeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeeee/MeMMe 88:8) ee eeeeee eee eeeeeeeee eeeeeeeeeeee; eeeee: 888 ee (88%). Meee eeeeeeeeeeee eee eeeeeeeee ee MeMM (88 eM) eee eeeee eeee 88 eeeee ee eeeee MMe ee ee. Mee eeeeeee eee eeeeeeee eee 8 e, eeeeee ee 8°M, eeeeeeeeeee eeee ee MeMMM8, eee eeee eeeeeeee. Mee eeeeeeee eee eeeeeeeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MM8Me8/MeMMe 8:8); eeeee: 888 ee (88%; 88% eee eeee eeeee).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) M 88e8, 8888.