Methoxybenzaldehydes

R B Woodward was one of the leading organic chemists of the middle part of the twenti eth century Known pnmanly for his achievements in the synthesis of complex natural products he was awarded the Nobel Pnze in chemistry in 1965 He entered Massachusetts Institute of Tech nology as a 16 year old freshman in 1933 and four years later was awarded the Ph D While a student there he earned out a synthesis of estrone a female sex hormone The early stages of Woodward s estrone synthesis required the conversion of m methoxybenzaldehyde to m methoxy benzyl cyanide which was accomplished in three steps... 

Suggest a reasonable three step sequence showing all necessary reagents for the preparation of m methoxybenzyl cyanide from m methoxybenzaldehyde... 

These trivial names may be retained citral (3,7-dimethyl-2,6-octadienal), vanillin (4-hydroxy-3-methoxybenzaldehyde), and piperonal (3,4-methylenedioxybenzaldehyde). 

Both -hydroxybenzaldehyde and its methyl ether, -methoxybenzaldehyde [123-11-5] (p-anisaldehyde) have found extensive use in electroplating. The most widespread appHcation has been in alkaline bright zinc plating, both in non-cyanide (77) and in cyanide-containing (78) baths. The aldehydes act as both brightening and leveling agents. 

In the flask are placed 60.8 g. (0.4 mole) of 2-hydroxy-3-methoxybenzaldehyde (Note 2) and 200 ml. of 2N sodium hydroxide (0.4 mole). The mixture is stirred until almost all the solid has dissolved. The stirrer is replaced by a dropping funnel which contains 284 ml. (0.5 mole) of 6% hydrogen peroxide (Note 3). With occasional shaking, the hydrogen peroxide is added in portions of 20-25 ml. About 1 hour is required for the addition the temperature is kept between 40 and 50°. After the addition of the first portion of hydrogen peroxide, the temperature rises to about 45° and a dark solution results. The temperature is allowed to fall to 40° before the next portion of the peroxide is added. 

Acetylmethionine nitrile [538-14-7] M 172.3, m 44-46°- Crystd from diethyl ether. 5-Acetyl-2-methoxybenzaldehyde [531-99-7] M 166.2, m 144°. Crystd from EtOH or Et20. 

Chloro-, hydroxy-, and methoxybenzaldehyde denvatives Denvatize with 2,4-dinitrophenylhydrazine solution in hydrochlonc acid Heat to 80 °C, cool and chromatograph [83]... 

Anhalonine and Lophophorine. Spath and Gangl showed that each of these alkaloids contains a methylenedioxy group and that the quarternary iodide prepared from dZ-anhalonine is identical with lophophorine methiodide so that lophophorine must be N-methylanhalonine. Anhalonine was synthesised from 3 4-methylenedioxy-5-methoxybenzaldehyde by condensation with nitromethane, reduction of the product to the corresponding -ethylamine, the acetyl derivative (VII) of which, on treatment with phosphoric anhydride, condensed to 6-methoxy-7 8-methylenedioxy-l-methyl-3 4-dihydrofsoquinoline, m.p. 60-2°. This, on reduction, furnished the corresponding tetrahydrofsoquinoline, which proved to be anhalonine (VIII), and on conversion to the quaternary methiodide the latter was found to be lophophorine (IX) methiodide. The possible alternative, 8-methoxy-6 7-methylenedioxy-l 2-dimethyl-l 2 3 4-tetrahydrofsoquinoline, was prepared by Freund s method and the methiodide shown not to be identical with lophophorine methiodide. 

CH3Q—CH — p-Methoxybenzaldehyde Ketones yield secondaiy alcohols ... 

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