Science of Synthesis

Schall, A.; Reiser, O., Science of Synthesis, (2007) 25, 645.

In 1876, Reimer and Tiemann reported the synthesis of hydroxyaldehydes from phenols in chloroform and aqueous alkali at 65–70°C.[‌140‌–‌142‌] 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).

‌Meeee 88‌ Mee Meeeee–Meeeeee Meeeeeee[‌888‌–‌888‌]

Meeee	Meeee	Meeeeee	Meeee (%)	Mee
8	eeeeee	8-eeeeeeeeeeeeeeeeeee +	88	[‌888‌–‌888‌]
		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	[‌888‌–‌888‌]
8	8-eeeeeeeeeeeee	8-eeeeeee-8-eeeeeeeeeeeeeeeeeee	88–88	[‌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 +	88–88	[‌888‌–‌888‌]
		8-eeeeeeeeeeeeeeeeee-8-eeeeeeeeeeee	8
88			88	[‌888‌]
88	eeeeeee	eeeeeee-8-eeeeeeeeeeee	88	[‌888‌–‌888‌]
88	eeeeeeeeeeeeeee	eeeeeeeeeeeeeee-8-eeeeeeeeeeee	88	[‌888‌]
88			88–88	[‌888‌,‌888‌]
88			88	[‌888‌]
88			88	[‌888‌]
88			88	[‌888‌]
88			88	[‌888‌]

Me eeeeeeee ee eee eeeee eeeeeee eeeeeeeee ee Meeeeeee ‌88.8.8.8‌–‌88.8.8.88‌, eeeeeeeeeee ee eee eeeee eeeee eeeee eeeee eeeee eeeeeeeeee. Mee eee eeee ee eee eeeeeeee ee eeeeeeeeeeeeeee, eeeeeeeee ee e eee-eeee 8,8-eeeeeeeeeee ee eeeeeeeeeeee eeee eeee eeeeeeeeee, ee eee eeeeeeeee eeeee, eeeeeeee ee eeeeeeeeee ee eee eeeeeee eeeeeeeeeeeeeeeee eeeeee (‌Meeeee 88‌).[‌888‌–‌888‌]

‌Meeeee 88‌ Mee Meeeee–Meeeeee Meeeeeee[‌888‌–‌888‌]

Mee ee eee eeeeeeeeee ee eee eeeeee eeeeeeee eeeeeeeeeeeeeee, eeee eeeeeeee eeee eee ee eeeeeeeee ee eeeeeee [8+8] eeeeeeeeeeeee ee eee eeeee eee eeeee eeeeee. Meeeeeeeeeee, eeeeeeeeeee eee ee eeeeeeee eeee eeee eeeeeeeeeeeeee eeeeeeeee eeee ee eeeeeeee eeeee eeeee,[‌888‌] eeeee eeeee eeee eee eeee eeeeeeee eeeee eee eeee-eeeeeeee eeeeeeee eeeeeeeee ee Meeeeeee ‌88.8.8.8‌–‌88.8.8.88‌.

Meeee eeee eeee e eeeeee ee eeeeeeee ee eeeeeee eee eeeeee eee eeeeeee eee eeeee ee eee Meeeee–Meeeeee 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 (8.8 eee%) 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 Meeeee–Meeeeee eeeeeeee.[‌888‌]

‌Meeee 88‌ Meeeee–Meeeeee Meeeeeee Meeee Meeeeeeeee[‌888‌]

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

Meeeeeeeeeee Meeeeeeee

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

Meee e 8-M eeeee-eeeeee, eeeee-eeeeeeee eeeee, eeeeee eeee e eeeeeee eeee eeeeeee, e eeee eeeeee eeeeeeeee, e eeeeeeeeee eeeeee, eee e eeeeeeeeeee, eeee eeeee 8-eeeeeeeeeeeee (888 e, 8 eee) eee e eee eeee ee MeMM (888 e) ee M8M (888 eM). (Me ee eeeeeeeeee ee eee eee MeMM eeee ee eee eeeeee eeeeeee eeeee eee eeeeee eee eeee eeeeeeeee ee M8M. Me eeee eee eee eee eeeeeeee eeee eeeeeee eeeeeeeee eee eeeeee eee eeeeee eeeeeeeee eeeeeeeee ee eeeeeee.) MMMe8 (888 e, 8 eee) eee eeeee eeeeeeee eeee eee eeee eee eeeeeee ee e eeeeeeeeeee ee 88°M, eee eeee eeeeeeeeeee eee eeeeeeeeee eeeeeeeeee eee eeeeeeee, eeeee eeeeeeee 8–8 e. Meee eee eee MMMe8 eee eeee eeeee, eee eeeeeee, eeeee eee eeeeee eeee eeeee eee eeeeee eeee e eeeee eeeeee, eee eeeeeee ee 88–88°M eee eeeeeee 88–88 eee. Mee eeeeeee eee eeeeee, eeeeeeeeeee ee e 8-M eeeee-eeeeeeee eeeee eeee eee eee ee eee M8M (888–888 eM), eeeeee eeeee, eee eeeeeeeee ee eeeeee ee eee eeeeeee eeeeeeee ee 88 M M8MM8 (888–888 eM). Mee 8-eeeeeee-8-eeeeeeeeeeeeeeeeeee eee eeeee-eeeeeeeee; eeee eeee eeeeeee, 8–8 M ee eeeeeeeeee eee eeeeeeeee. Mee eeeeeeee, eeeee eee e eeeeee eee, eee eeeeeeeee eeee eee eeeeeeeeee eeee Me8M. Mee eeeeeeee eeee eeeee (Me8MM8) eee eee eeeeeee eee eeeeeee. Mee eeeeeeee eeeee eeeee eee (888–888 e, 88–88%) eee eeeeeeeee eeeee eeeeeeeeee eeeeeeee ee ee eeeeeeeeee ee M8 ee eeee eeee 8-eeeeeee-8-eeeeeeeeeeeeeeeeeee; ee 888°M/88 Meee.

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

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

Meeeeeeeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee Meeee Meeeeeeeee:[‌888‌]

Mee eeeee eeeeee, 8-eeeeeeeeeee eeeeee (8 eeee), 88% ee MeMM (8.8 eM, 88 eeee) eee MMMe8 (88 eeee, 88 eM) 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 8 M MMe. Mee MMMe8 eeeee eee eeeeeeeee eee eeeeeeee ee MMM. Meee eee eeeeeeee eee eeeeeeee, eee eeeeeee eee eeeeeeeee ee eM 8 eeee 8 M 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

Meeeeee Meeeeeeeeee

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