Dihydroxybenzaldehyde

Synthesis of complex 1. The pentadentate salen catalyst 1 was synthesized as described (9). In short, the tosylated 2-[2-(2-methoxyethoxy)-ethoxy]-ethanol 2 (10) was reacted with 2,4-dihydroxybenzaldehyde 3 to yield 4-alkoxy salicylaldehyde 4 after chromatographic purification (eq. 1). Subsequent condensation of 4 with 1,3-diaminopropanol yielded water-soluble salen ligand 5 in sufficient purity and 89% yield (11). The formation of an azomethine bond is indicated by a shift of the NMR signal for the carbonyl carbon from 194.4 ppm in aldehyde 4 to 166.4 ppm for the imino carbon in 5. The pentadentate ligand 5 was then treated with copper(ll) acetate in methanol to obtain the dinuclear copper(ll) complex 1 as a green solid (eq. 2) (11). 

C7H7NO3 Resorcylaldoxime (2,4-Dihydroxybenzaldehyde oxime) Metallochromic indicator Fe 3... 

Dihydroxybenzaldehyde 5 9 0 A reaction flask (500-ml capacity) is fitted with an efficient stirrer, a reflux condenser, and a wide gas-inlet tube the end of the condenser is connected to, successively, a wash-bottle containing sulfuric acid, an empty safety flask, and a tube that passes over the surface of a sodium hydroxide solution. Resorcinol (20 g) and anhydrous ether (150-200 ml) are placed in the reaction flask, and anhydrous zinc cyanide (1.5 equivalents) is added. Then a rapid stream of dry gaseous hydrogen chloride is passed in. The zinc cyanide disappears as a milky mixture is formed and as the hydrogen chloride dissolves, the imide hydrochloride condensation product separates as a thick oil which solidifies in 10-30 min. The ether is usually saturated in 1.5 h, after which hydrogen chloride is passed in slowly for a further 0.5 h. Then the ether is decanted, water (100 ml) is added to the imide hydrochloride, and the solution is heated to the boiling point, filtered and allowed to cool. About half the aldehyde separates. After this has been collected the remainder of the aldehyde crystallizes in 10-15 h. The total yield is about 95 %, and the m.p. is 135-136° after recrystallization with charcoal from water. 

A more specific route (ref.46) to osthenol from which racemic meranzin, isomeranzin and auraptenol were obtained commenced with 2,4-dihydroxybenzaldehyde. By its reaction with 2-methylbut-3-en-2-ol in the... 

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