Yes, that Zn/Hg reduction has quite an awful yield but at least the materials are available and I know it works (unlike my chloromethylation reaction.) Perhaps the procedure can be tweaked and I can do it better than old shulgin
I am also suprised at the high quantities of reagents needed for this reduction. 150g of zinc and 15g of mercuric chloride for that kind of yield? Perhaps I should try the Al/Ni reduction instead..
nicodem: I know the chloromethylation reaction is sketchy at best. Sorry for the lack of references, most all can be found on rhodium.
The oxidation of benzyl alcohols to aldehydes in solvent free conditions
was on rhodium but now I can't find it and only have a printed copy. I believe it's from Tetrahedron. It involves the use of copper sulfate pentahydrate and alumina with KMnO4, however they don't use CuSO4 for the oxidation of benzyl alcohols. KMnO4 is simply mixed with alumina and the alcohol is added and everything is stirred magnetically for 45 mins. An organic solvent is then added and the product extracted.
I know this reaction works, I've performed it before to create piperonal from 3,4-methylenedioxybenzyl alcohol.
There is no reference for the chloromethylation of 2,5-dimethoxybenzaldehyde, I was just hoping it was going to work.
I cited the reduction of the benzyl chloride in another post. I may just end up going that route, here is a reference for the chlorination of benzyl alcohol:
https://www.thevespiary.org/rhodium/Rhodium/chemistry/pea.benzyloh.html
"p-Anisyl alcohol (100 g, 0.725 mole) was shaken with 500 ml of concd HCl for 2 min. The organic phase was washed with H20, 5% NaHCO3 and H2O"
The mandelic acid patents can easily be found by doing a search on this forum.
The formation of the aldehyde from benzyl chloride, NaOH/KOH, and 2-nitropropane can be found here:
https://www.thevespiary.org/rhodium/Rhodium/chemistry/halide.carbonyl.html
"In a 200-ml. two-necked flask fitted with a mechanical stirrer and a reflux condenser, 14 g. (0.25 mole) of potassium hydroxide was dissolved in 25 ml. of water. 2-Nitropropane (22.2 g., 0.25 mole) was added, and the hot mixture stirred to a clear yellow solution. Benzyl chloride (31.7 g., 0.25 mole) was added, and the mixture stirred and heated under reflux for two hours. After cooling, the mixture was filtered through a glass wool plug to remove precipitated potassium bromide, washing with 50 ml. of ether. The ether layer was separated, washed with 25 ml. of water, dried over magnesium sulfate, and distilled. A small amount of acetoxime crystallized in the condenser (b.p. 52°C (18 mm.)), m.p. and mixed m.p. 61-62°C. The benzaldehyde was collected at 62°C (1 mm.), 13 g. (49%); phenylhydrazone, m.p. 157-158°C.7"
The formation of the nitrostyrene with cyclohexylamine and nitroethane can be found under the MDMA synthesis in PiHKAL and the reduction he uses on the ketone is almost the same way to reduce a nitro compound, no amination is required though of course.