M-Methoxybenzaldehyde

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... 

Aldol condensation of the methoxymethyl ether of m-methoxybenzaldehyde (83) with cyclohexanone affords the conjugated ketone 84. Michael addition of dimethyl amine leads to the ami noketone Reduction of the ketone... 

MS fragmentation of a series of 13 4-aryl-3,3-dichloro-2-oxetanes (18) has been reported to give the dichloroketene cation as the base peak in every case, except for the 4-(m-methoxyphenyl) compound. There the base peak was for the m-methoxybenzaldehyde cation. The results were in marked contrast to the cleavage seen on thermolysis, which gave carbon dioxide and the corresponding/3,j8-dichlorostyrene (78JHC1165). 

Sonawane et al. (Sonawane et al., 1994) described a practical and efficient synthesis of fenoprofen using commercially available m-phenoxybenzaldehyde as the starting material. The key step in the synthesis is the transformation of the a-hydroxyacetal (i) into its chlorosulfonyl ester in situ and its concomitant rearrangement to the methyl ester (ii) in high yields. The required a-hydroxyacetal (i) can be readily prepared from m-methoxybenzaldehyde by the routine sequence of reactions Grignard reaction with ethyl bromide or chloride, oxidation and finally a-chlorination with CuCI2-LiCI/DMF. 

An unfortunate oversight was that the m-methoxybenzaldehyde had to be custom manufactured, and orders for many thousands of pounds were placed before it was realized that it would no longer be needed. So CDM-HABI was manufactured for another year, mostly because no one had the courage to throw it out and make the better Dylux proof paper with the new HABI. In spite of the fact that this resulted in excess of 1,000,000 savings on production costs of Dylux proof paper, almost 4 years were required before CDM-HABI was replaced. 

B. m-Methoxybenzaldehyde. The crude wi-hydroxybenzalde-hyde is dissolved in about 550 ml. of 2 A7 sodium hydroxide in a 2-1. three-necked flask equipped with a mechanical stirrer, a thermometer, and a 125-ml. dropping funnel. The dark-colored solution is stirred while 126 g. (95 ml., 1 mole) of methyl sulfate (Note 3) is added dropwise and the temperature is maintained at 40-45°. When the addition is complete the mixture is stirred for 5 minutes. A 275-ml. portion of 2 N sodium hydroxide (Note 4) is added in one lot, and then 63 g. (47.5 ml.) of methyl sulfate is added as before, except that the temperature is allowed to rise to 50°. Stirring at 50° is continued for 30 minutes, the mixture is cooled, and the organic layer is extracted w ith ether (Note 5). The ether solution is dried over anhydrous sodium sulfate for 8 hours, then filtered and concentrated by distillation. The residue is distilled under reduced pressure. The yield of w -methoxybenzaldehyde, a pale yellow liquid boiling at 88 90°/3 mm., is 86 98 g. (03 72 %,) (Note 6). 

Synonyms m-Anisaldehyde Vanillic aldehyde Lioxin 3-Methoxy-4-hydroxybenzaldehyde p-Hydroxy-m-methoxybenzaldehyde Lioxin Vanillaldehyde Vanillic aldehyde 2-Methoxy-4-formylphenol 3-Methoxy-4-hydroxybenzalde-hyde Vanilla Protocatechualdehyde, methyl- Zimco p-Vanillin Methylprotcatechuic aldehyde Methylprotocatechuic aldehyde Chemical/Pharmaceutical/Other Class Essential oil... 

Jakobsons, J., J. Gravitis, and V. G. Dashevskii. 1981. Theoretical analysis of conformations of lignin model compounds Studies of internal rotation, the relative stability of rotamers and an intramolecular hydrogen bond in vanillin and m-methoxybenzaldehyde molecules. Zh. Strukt. Khim. 22(2) 43-51. 

Anisaldehyde. See p-Anisaldehyde 2-Anisaldehyde. See o-Methoxybenzaldehyde m-Anisaldehyde. See m-Methoxybenzaldehyde o-Anisaldehyde. See o-Methoxybenzaldehyde p-Anisaldehyde... 

Saccharomyces lysate extract anti-inflammatory drug synthesis m-Methoxybenzaldehyde anti-irritant, anionics Disodium oleth-3 sulfosuccinate anti-irritant, antiperspirants Laureth-12 Laureth-23 anti-irritant, conditioners Hydrolyzed wheat protein anti-irritant, cosmetics Diammonium dimethicone copolyol sulfosuccinate Disodium ricinoleamido MEA-sulfosuccinate Ethyl hydrolyzed keratin Hydrolyzed almond protein Hydrolyzed collagen... 

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