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25.6.6.7 Method 7: Formylation of Aromatic Compounds with Hexamethylenetetramine

DOI: 10.1055/sos-SD-025-00443

Schall, A.; Reiser, O.Science of Synthesis, (200725630.

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.

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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 8888 [‌88‌]
8:8 M 88 [‌88‌]
8:8 M 88 [‌88‌]
8:8 M 88 [‌88‌]
8:8 M 88 [‌88‌]

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e Meeeee eeee, 888888°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 (88e, 8.888eee), 88 (88.8e, 8.888eee), eee MeMM (888eM) eee eeeeeee ee 888°M eee 8e eeeee M8. Meeee eeeeeee ee 88°M, 88% ee M8MM8 (888eM) eee eeeee, eee eeeeeeee eee eeeeeeeee ee 888°M eee 8e. Mee eeeeeeeee eeeeeee eee eeeeeeeee eeee Me8M (8×88eM), eee eee eeeeeee eee eeeeee eeee M8M (8×88eM) 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: 88.8e (88%); ee 8888°M.

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

M eeeeeee ee 8,8-eeeeeee (88.8e, 888eeee), 88 (88.8e, 888eeee), eee MMM (888eM) eee eeeeeeee (8888°M) eee 88e. Mee eeeeeeee eeee eeeeeeeeeeee eee eeeeeeee eeee eee eeeee (888eM), eee eee eeeeeeeee eeeeeee eee eeeeeee eee 88eee, 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: 88.8e (88%); ee 888888.8°M.

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

Meeeeeee 88 (888ee, 8.88eeee) eee eeeee ee e eeee ee 8-(eeeeeeeee)-8-eeeeeee-8-eeeeeeeeeeeee (888ee, 8.88eeee) ee MeMM (88eM), eeeee eee eeeeee ee 888°M eee 8e. 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: 888ee (88%); ee 8888°M (Me8M).

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