Science of Synthesis

Schall, A.; Reiser, O., Science of Synthesis, (2007) 25, 630.

The employment of hexamethylenetetramine (‌26‌) as a formylation agent, usually in combination with glyceroboric acid, is known as the Duff reaction.[‌87‌] Highly activated arenes such as phenols can be formylated in this way to give 2-hydroxybenzaldehyde derivatives ‌35‌; however, yields are generally low. A significant improvement uses the activation of hexamethylenetetramine with trifluoroacetic acid, allowing the formylation of a variety of aromatic compounds, including simple ones (‌Scheme 17‌).[‌89‌] The required conditions are mild, and good yields with a high preference for the formation of 1,4-aromatic aldehydes are observed. Acetic acid, often in combination with sulfuric acid used for the hydrolysis step, is also recognized as a suitable activator.

‌Meeeee 88‌ Meeeeeeeeee ee Meeeee ee Meeeeeeeeeeeeeeeeeeeee eee Meee[‌88‌–‌88‌]

‌Meeeeeeeeee 88‌

Meeeeeeee	Meeee (‌88‌/Meeeeeeee)	Meeeee	Meeee (%)	Mee
8-e-MeM8M8	8:8	M	88	[‌88‌]
8,8-Me8M8M8	8:8	M	88	[‌88‌]
8-Mee	8:8	M	88e	[‌88‌]
Me	8:8	Me	88	[‌88‌]
	8:8	M	88	[‌88‌]
8-MeMM8M8	8:8	M	88e	[‌88‌]
	8:8	M	88	[‌88‌]
	8:8	M	88	[‌88‌]
	8:8	M	88	[‌88‌]
	8:8	M	88	[‌88‌]
	8:8	M	88	[‌88‌]
	–	M	8	[‌88‌]
	8:8	M	88	[‌88‌]
	8:8	M	88–88	[‌88‌]
	8:8	M	88	[‌88‌]
	8:8	M	88	[‌88‌]
	8:8	M	88	[‌88‌]
	8:8	M	88	[‌88‌]

e Me e eeeeeee ee eee 8,8- (88%) eee 8,8- (88%) eeeeeee.

e Meeeee eeee, 888–888°M.

e Meee eeeeee eeee eee(8-eeeeeeeeeeee) eeeee (88%).

Meeeeeeeeeee Meeeeeeee

8-eeee-Meeee-8-eeeeeee-8-eeeeeeeeeeeeeeeeee (‌88‌, Me8 = 8-e-Me-8-MM-8-MeM8M8):[‌88‌]

M eeeeeee eeeeeeeeee 8-eeee-eeeee-8-eeeeeeeeeeee (88 e, 8.888 eee), ‌88‌ (88.8 e, 8.888 eee), eee MeMM (888 eM) eee eeeeeee ee 888°M eee 8 e eeeee M8. Meeee eeeeeee ee 88°M, 88% ee M8MM8 (888 eM) eee eeeee, eee eeeeeeee eee eeeeeeeee ee 888°M eee 8 e. Mee eeeeeeeee eeeeeee eee eeeeeeeee eeee Me8M (8 × 88 eM), eee eee eeeeeee eee eeeeee eeee M8M (8 × 88 eM) eee eeeee (MeMM8). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeeee e eeee eeeeee eee eeeee eeeeeeeeee MeMM. Mee eeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (MMMe8) ee eeee eee eeee eeeeeee ee e eeeeee eee, eeeee eeeeee eeeeeeeeeeee; eeeee: 88.8 e (88%); ee 88–88°M.

8-Meeeeee-8,8-eeeeeeeeeeeeeeeeeeee (‌88‌, Me8 = 8-MM-8,8-Me8M8M8):[‌88‌]

M eeeeeee ee 8,8-eeeeeee (88.8 e, 888 eeee), ‌88‌ (88.8 e, 888 eeee), eee MMM (888 eM) eee eeeeeeee (88–88°M) eee 88 e. Mee eeeeeeee eeee eeeeeeeeeeee eee eeeeeeee eeee eee eeeee (888 eM), eee eee eeeeeeeee eeeeeee eee eeeeeee eee 88 eee, eeee eeeee eeee Me8MM8, eee eeeeeeeee eeee Me8M. Meeeeee eeeee eeeeeee eeeeeeee ee eee Me8M eeee e eeeeee eeeee, eeeee eee eeeeeeeeeeeeee (MMMe8/eeeeeee) ee eeeeee eee eeeeeee; eeeee: 88.8 e (88%); ee 888–888.8°M.

8-(Meeeeeeee)-8-eeeeeee-8-eeeeeee-8-eeeeeeeeeeeeeeeeee (‌88‌, Me8 = 8-MeM-8-MM-8-Me-8-MeMM8M):[‌88‌]

Meeeeeee ‌88‌ (888 ee, 8.88 eeee) eee eeeee ee e eeee ee 8-(eeeeeeeee)-8-eeeeeee-8-eeeeeeeeeeeee (888 ee, 8.88 eeee) ee MeMM (88 eM), eeeee eee eeeeee ee 888°M eee 8 e. Meeee eeeee eeeeee ee eeeeeee eeeeeeeeeee, eee eeee eee eeeeeeee eeee M8M, eee eee eeeeeee eee eeeeeeeee eeee MeMMe. Mee MeMMe eeeee eee eeeeee eeee M8M eee eeeee, eeeee (Me8MM8), eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeee 8:8) ee eeee eee eeeeeee; eeeee: 888 ee (88%); ee 88–88°M (Me8M).

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) M 8, 888.