Science of Synthesis

Schall, A.; Reiser, O., Science of Synthesis, (2007) 25, 636.

Chloroiminium salts ‌36‌, generated by addition of gaseous hydrogen chloride to anhydrous hydrogen cyanide in the presence of aluminum trichloride or zinc(II) chloride, are highly reactive formylating reagents (‌Scheme 20‌). This process, known as the Gatterman reaction, is especially useful for the formylation of phenols and hetarenes (‌Table 17‌);[‌4‌] however, in contrast to the Vilsmeier–Haack reaction, discussed in Section ‌25.6.6.4‌, aromatic amines are not compatible substrates. In return, already weakly activated benzenes such as xylenes can be formylated in good yields (‌Table 16‌). The isolation of the resulting aldehydes in pure form is especially facile, because the aldiminium salt ‌37‌ often precipitates from the reaction mixture and can then be isolated by simple filtration and subsequently hydrolyzed to give the aromatic aldehyde.

Meeeeeeeeee, eeeeee eeeeeee eee ee eeeeeeee ee eeeeeeeeeeee ee eeee eeeeeee ee eeeeeeee eeeeeee (Meeeee–Meeeee eeeeeeeeeeee).[‌888‌]

‌Meeeee 88‌ Mee Meeeeeeeee Meeeeeee[‌8‌]

‌Meeee 88‌ Meeeeeeeee Meeeeeeeeee ee Meeeeeeeeee Meeeeeeeeeeee[‌88‌,‌888‌–‌888‌]

Meeee	Me8	Meeeeeee	Meeee (%)	Mee
8	8,8-Me8M8M8	MMe, MMM, MeMe8	88	[‌888‌]
8	8,8-Me8M8M8	MMe, MMM, MeMe8	88	[‌888‌]
8	8-MMM8M8	MMe, MMM, MeMe8	88	[‌888‌,‌888‌]
8	8-MeMM8M8	MMe, Me(MM)8, MeMe8	88	[‌888‌,‌888‌]
8		MMe, Me(MM)8, MeMe8	88	[‌888‌]
8		MMe, Me(MM)8	88	[‌888‌]
8		MMe, Me(MM)8, MeMe8	88	[‌888‌]
8	Mee	MMe, Me(MM)8, MeMe8	88–88	[‌888‌]
8		MMe, MMM, Me(MM)8	88	[‌888‌]
88		MMe, Me(MM)8, MeMe8	88	[‌88‌]
88		MMM, MeMe8, MMe	88–888	[‌888‌]

‌Meeee 88‌ Meeeeeeeee Meeeeeeeeee ee Meeeeeeeee Meeeee eee Meeeeeeee[‌888‌,‌888‌–‌888‌]

Meeee	Meeeeeeee	Meeeeeee	Meeee (%)	Mee
8		MMe, Me(MM)8	88	[‌888‌]
8		MMe, MMM, MeMe8	88	[‌888‌,‌888‌]
8		MMe, MMM, MeMe8	88	[‌888‌]
8		MMe, MMM, MMMe8	88	[‌888‌]
8		MMe, MMM, Me8M	88	[‌888‌]
8		MMe, MMM, MeMe8	88	[‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeee-8,8-eeeeeeeeeeeeeeeeeeee (‌Meeee 88‌, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

MMMMMMM: Meeeeeee eeeeeeeeeee eeee ee e eeeeee eeeeeeee ee eee eeeeeee eee eeeeee eeeeeeeee eeee eeeee.

8,8-Meeeeeeeeeeeeee (88.8 e, 8.888 eee) eee eeeee ee eeeeeeeeeeeeeeeee (888 eM) eee eeeeeeeeee ee 88°M. Me(MM)8 (88.8 e, 8.888 eee) eee eeeee, eee MMe(e) eee eeeeeee eeeeeee eee eeeeeee eeee eeeeeeee. Mee eeee ee MMe(e) eeeeeeee eee eeeeeeee ee eeeee eee MMe eeeeeeeeee. Meeee 8 e ee MMe(e) eeeeeeee, eee eeee ee eeeeeeeeee eeeeeeeeeeeee eeeeeeeee eee MeMe8 (88.8 e, 8.888 eee) eee eeeee. M eeee eeee ee MMe(e) eeee eee eeeeeeeeee. Mee eeeeeeeeeee eee eeeeeeeee ee 88°M eee eeeeeeeeee ee eeee eeeee eee 8 e. Mee eeeeeee eee eeee eeeeee eeee e eeeeeee ee eee (888 eM) eee eeeee MMe (888 eM). Mee eeeeeeee ee eee eeeeeeee eeeeee eeee eeee eeeeee eeee MMMe8 (8 × 888 eM) eee eeeee ee eee eeeeeee eeeee. Mee eeeeeeeee eeeeeeee eeeee eee eeeeeee ee 88–88°M eeeeeeeee. Mee eeeeeee eeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeee eeee MMMe8 (888 eM eee 888 eM). Mee eeeeeeee eeeeeeee eeee eeeeee eeee eeeeeeeee M8M (8 × 888 eM), eee eee eeeeeee eeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeeeeeee eee eeeeeeeeeee ee e eeeeeeeeeeee eeeee eeeeeeee eeee e Meeeeee eeeeee eee eeeeeeeee (888°M/8.8 Meee) ee eeee e eeeeeeeeee (88.8 e) eeeeeeeeee eeeeeeee eeeeeeeeeeeeeeeee eee e 8:8 eeeeeee ee eee eeeeeee 8-eeeeeee-8,8-eeeeeeeeeeeeeeeeeeee eee 8-eeeeeee-8,8-eeeeeeeeeeeeeeeeeeee. Mee eeeeeeeeee eee eeeee ee e-MeMMe eee eeeeeeeeeeee eeeeeeeee ee 8°M. Mee eeeeeeee eeee eeeeeeeee ee eeeeeeeeee eee eeeeee eeee MeMMe/eeeeee (8:88, 8 eM) ee eeee 8-eeeeeee-8,8-eeeeeeeeeeeeeeeeeeee (8.88 e). Mee eeeeee eeeeee eee eeeeeeeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:88) ee eeee ee eeeeeeeeee 88.88 e; eeeee: 88.88 e (88%).

8-Meeeeee-8-eeeeeeeeeeeeeeeeee (‌Meeee 88‌, Meeee 88); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeeee eeeeeee eee ee eeeeeeee eeeeeee eee eeee eee ee eeeeeeeee eeeee.

MMMMMMM: Meeeeeee eeeeeeeeeee eeee ee e eeeeee eeeeeeee ee eee eeeeeee eee eeeeee eeeeeeeee eeee eeeee.

MMe(e) eee eeeeee eee 88 eee eeeeeee e eeeeeee ee eeeee MMM (88 e, 8.88 eee) eee 8-eeeeeeeeeeeee (88 e, 8.88 eee) eeeeee ee ee eee eeee. MeMe8 (88 e. 8.88 eee) eee eeeee eeeeeeeee. Meeee eeeeee eeeeee eeee MMe, eee eeeeeeeeeee eee eeeeee ee 88°M eee eeeeeeeeee eee 8–8 e. Mee eeeeeee eee eeeeee eeee eee eee MMe. Mee eeeeeeeee eeeeeeeeeee eee eeeeeeee ee MMe. Mee eeeeeeee eee eeeee eeeeeeeee eee eeee eeeeeee eeee MeMMM8 eeee. Mee eeeeeeeee eeeeeeee eeeeeee eee eeeeeeeee ee eeeeeeeeee eee eeeeeeeeee eeee ee Me8MM8. Mee eeeeeeee eee eeeeeeee ee e eeeeeeeee eee; eeeee: 88–88 e (88–888%); ee 888°M.

References

Meeeeee Meeeeeeeeee

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