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25.6.6.13 Method 13: The Reimer–Tiemann Reaction

DOI: 10.1055/sos-SD-025-00443

Schall, A.; Reiser, O.Science of Synthesis, (200725645.

In 1876, Reimer and Tiemann reported the synthesis of hydroxyaldehydes from phenols in chloroform and aqueous alkali at 6570°C.[‌140‌‌142‌] In this reaction, mainly the ortho-hydroxyaldehyde is formed together with small amounts of the para-isomer, which can be suppressed if pyridine is used as the base.[‌143‌] The scope of the reaction is limited; besides phenols, only certain heterocyclic compounds such as indoles or pyrroles can be employed as substrates, and yields do not generally exceed 50% (Table 19).

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Meeee Meeee Meeeeee Meeee (%) Mee
8 eeeeee 8-eeeeeeeeeeeeeeeeeee + 88 [‌888‌‌888‌]
8-eeeeeeeeeeeeeeeeeee 88
8 8-eeeeeeeeeeeeee 8-eeeeeee-8-eeeeeeeeeeeeeeeeee + 88 [‌888‌,‌888‌]
8-eeeeeee-8-eeeeeeeeeeeeeeeeee 8
8 8-eeeeeeeeeeeeee 8-eeeeeee-8-eeeeeeeeeeeeeeeeee 88 [‌888‌]
8 8-eeeeeeeeeee 8-eeeee-8-eeeeeeeeeeeeeeeeeee 88 [‌888‌]
8 8-eeeeeeeeeeee 8-eeeeeee-8-eeeeeeeeeeeeeeeeee 88 [‌888‌]
8 8-eeee-eeeeeeeeeee 8-eeee-eeeee-8-eeeeeeeeeeeeeeeeeee 88 [‌888‌]
8 8,8-eeeeeeeeeeeeee 8,8-eeeeeeee-8-eeeeeeeeeeeeeeeeeee 88 [‌888‌‌888‌]
8 8-eeeeeeeeeeeee 8-eeeeeee-8-eeeeeeeeeeeeeeeeeee 8888 [‌888‌,‌888‌]
8 8-eeeeeeeeeeee 8-eeeeee-8-eeeeeeeeeeeeeeeeeee + 88 [‌888‌]
8-eeeeee-8-eeeeeeeeeeeeeeeeeee 88
88 8-eeeeeeeeeeee 8-eeeeee-8-eeeeeeeeeeeeeeeeeee + 88 [‌888‌]
8-eeeeee-8-eeeeeeeeeeeeeeeeeee 88
88 8-eeeeeeeeeeee 8-eeeeee-8-eeeeeeeeeeeeeeeeeee 8 [‌888‌]
88 8-eeeeeeeeeeee 8-eeeeee-8-eeeeeeeeeeeeeeeeeee 88 [‌888‌,‌888‌]
88 8,8-eeeeeeeeeeeeee 8,8-eeeeeeee-8-eeeeeeeeeeeeeeeeeee 88 [‌888‌]
88 8-eeeeeeee 8-eeeeeeeeeeeeeeeeee-8-eeeeeeeeeeee + 8 [‌888‌,‌888‌]
8-eeeeeeeeeeeeeeeeee-8-eeeeeeeeeeee 8
88 8-eeeeeeee 8-eeeeeeeeeeeeeeeeee-8-eeeeeeeeeeee + 8888 [‌888‌‌888‌]
8-eeeeeeeeeeeeeeeeee-8-eeeeeeeeeeee 8
88 88 [‌888‌]
88 eeeeeee eeeeeee-8-eeeeeeeeeeee 88 [‌888‌‌888‌]
88 eeeeeeeeeeeeeee eeeeeeeeeeeeeee-8-eeeeeeeeeeee 88 [‌888‌]
88 8888 [‌888‌,‌888‌]
88 88 [‌888‌]
88 88 [‌888‌]
88 88 [‌888‌]
88 88 [‌888‌]

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Meeee eeee eeee e eeeeee ee eeeeeeee ee eeeeeee eee eeeeee eee eeeeeee eee eeeee ee eee MeeeeeMeeeeee eeeeeeee. Meeeeeeeee ee eeeeeeeeee ee eeee eeeee; eeeeeee, eee eeeeeeee eeeeeee eeeeee ee ee eeeeeeee eeeeeee, eee eeeeeeee, eee eeeeee ee eeeeeeeeee eeeee ee ee ee eeeeeeeee eeeeee eee eee eeeeeee ee e eeeee eeeeeeeeeeeeee, eeee ee ee eee eeeeeeeee ee eeeeeeee eeeeeeeee 88 (Meeee 88).[‌888‌] M eeeeee ee eeeeeeeee eee eeeeeeeee eeee eeee eeeeee eeee ee eeeeeeeeeeeee,[‌888‌,‌888‌] eeeeeeee eeeeee, ee eeeeeeeeee eeeeeeee eeeee.[‌888‌] Mee eeeeee, eeeee eeeeeeeee eee eeee eeeeee eeeee-eeeeeeee eeeeeeeee ee eeeeeeeeeee eeeeeeee eeeeeeeeeeeeeee eeee eeeeeeeeee eee eeeeee eeeeeeeee, eee ee eeeeeeee ee eee eeeeeeee eeeeee, eeeeeeeeeee eee eeee eeeeeeeeeee. Meeeeee, eeeeeeeee eeeeeee ee eeeeeeeeeeeeee (8.8eee%) eeeeeeeeeeeee eeeeeeee eee eeeee eee eee eeeeeeeee ee eeeeeeeeeeeeeeee eeee eeeeeee. Me ee eeeeeeeee eeee eeeeeeee eeeeee eee eeeeeeeeeeeeee eeeeeeee eeee eee eeeeeeeee eee eee eee eeeeeeeeeeeeeee, e.e. ee eee eeeeeeeee ee eeeee [(M88MMMMe8)+MeM]. Mee eeeeeeee ee eeeee eeeeeeee eee eeee eeee e eeeeeeeeeee eeeeee ee eee MeeeeeMeeeeee eeeeeeee.[‌888‌]

Meeee 88 MeeeeeMeeeeee Meeeeeee Meeee Meeeeeeeee[‌888‌]

M Meee Meeeeee Meeee (%) Mee
Meeeeeeeee Meeeeeeeeeee Meeeeee
MMe 8e M 88 88 [‌888‌]
Me 8e M 88 88 [‌888‌]
Me 88e M 88 88 [‌888‌]
Me 8e M 88 88 [‌888‌]
Me 8e M 88 88 [‌888‌]
Me 8e M 88 88 [‌888‌]
Me 8.8e M 88 88 [‌888‌]
Me 8e M 88 88 [‌888‌]
MMe 8e M 88 88 [‌888‌]
Me 8e M 88 88 [‌888‌]
Me 8e M 88 88 [‌888‌]
Me 8e M 88 88 [‌888‌]
MMe 8.8e M 8 88 [‌888‌]

e Meeeee M: Meeeeee eeee eeeeeee, 888M, eeeeeeee MeMM; M: Meeeeee Meee Meeeeeeee, 888M, eeeeeeee MeMM; M: Meeeeee Meee Meeeeeeee, 888M, 88% ee MeMM; M: Meee Meeeeee Meeeeeee, 888M, 88% ee MeMM; M: Meee Meeeeee Meeeeeee, 888M, 88% ee MeMM, eeeeeeee eeeeeeee.

Meeeeeeeeeee Meeeeeeee

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

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M-(eeee-Meeeeeeeeeeeee)-8-eeeeee-M-eeeeeeee (Meeee 88, Meeee 88):[‌888‌]

Meeeeeee MeMM (8.88e, 88.88eeee) eee eeeee ee e eeeeeeeeee ee M-(eeee-eeeeeeeeeeeeee)-M-eeeeeeee (8e, 8.88eeee), M8M (8.888eM, 88.88eeee), eee MMMe8 (88eM). Mee eeeeeee eee eeeeeeee eee 8e. Meeeeeeeee MeMM (8.88e, 88.88eeee) eee eeeee eeeee 8 eee 8.8e. Mee eeeeeee eee eeee eeeeeee eeee M8M eee MeMMe, eee eee eeeeeee eeeee eee eeeeeeeee ee eM8 eeee 8M MMe eee eeeeeeeee eeee MeMMe. Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee eeeee, eeeee (MeMM8), eee eeeeeeeeeeee. Meeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MMMe8/MeMM 88:8 eeee 8% MeMM) eeeeeeee eee eeeeeee eeeeeee ee e eeeee eee; eeeee: 8.88e (88%).

Meeeeeeeeeeeeeeeee 88; Meeeeee Meeeeeeee Meeee Meeeeeeeee:[‌888‌]

Mee eeeee eeeeee, 8-eeeeeeeeeee eeeeee (8eeee), 88% ee MeMM (8.8eM, 88eeee) eee MMMe8 (88eeee, 88eM) eeee eeeeee ee e eeeeeeee eeeee eeee e eeeeeeee eeeeeee eee eee eeeee eee eeeeeeee ee ee eee eeee. Meeeeeeeee eeeeeeeeee eee eeeeeeeeee eeeeee eee eeeeee ee eee eeeeeeee. Meeeeeee eeee eeeeeee ee eeeeeee eee eeeeeeeee eeee 8M MMe. Mee MMMe8 eeeee eee eeeeeeeee eee eeeeeeee ee MMM. Meee eee eeeeeeee eee eeeeeeee, eee eeeeeee eee eeeeeeeee ee eM8 eeee 8M MMe eee eee eeeeeee eeeee eee eeeeeeeee. Mee eeeeeee eeeee eee eeeeee eeee Me8M (8×) eee eee eeeeeee eeeeee eeee eeeeeeee eee eeeee (MeMM8). Mee eeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MM8Me8). Meeee eeeeeeeee eeeeeeeeee eeeeeee eeee eeeeeeee eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeeee e eeee eeeeeee.

References