fastandbulbous; The N-methyl analogues of both IAP and NAP (naphthyl-amino-propane, I just made that up for lack of a better term.) interest me as well. What interests me even more is the alpha-ethyl and N-methyl-alpha-ethyl analogues. There is no doubt that MBDB/BDB are fascinating compounds and I would expect more of the same. There's no reason not to synthesize these when synthesis is no more difficult; merely substituting 1-nitropropane for nitroethane in the condensation.
Lilienthal; actually, you are right, but it was only an error of mine. It is phosphorus
tetrahalide (PBr5 or PCl5) that is required for this reaction to take place. I don't have any online references for this reaction; nor have I searched for them. This is in an organic chemistry book of mine:
Noller, Carl R. (Carl Robert), Chemistry of organic compounds [by] Carl R. Noller. Hah, I know this is ancient but it is a great book with tons of information on heterocyclics. And since it was written before the "drug war" hysteria set in it is quite liberal in this area. Routes to several barbituates and amphetamine are provided (no substituted phenethylamines, although mescaline is briefly mentioned.) LSD is briefly mentioned as a compound that produces a psychosis much like schizophrenia.
I would rather not just purchase the aldehyde because I am interested in the chemistry in getting to that point, and also because simply buying the aldehyde may not always be an option for me.
nicodem; okay, here is a brief overview of how I did the chloromethylation. A mixture of HOAc, an equimolar amount of formalin solution, and a catalytic amount of phosphoric acid was saturated with HCl gas. When the substrate was added under stirring the mixture was quite heterogenous so a PTC was also added. This was allowed to stir rapidly at room temperature for 24-36 hours (probably excessive, but it was the next time I could get back to the lab.) At this point the mixture had changed to a much lighter yellow color. The reaction was flooded with ice-cold dH2O and allowed to stir for 15 minutes and the product precipitated as a yellow solid which was isolated by vacuum filtration.
Formylation went like this: To a solution of water and 2-nitropropane (equimolar to the substrate) was added a saturated equimolar NaOH solution. This was allowed to stir at room temperature for 1 hour. The substrate dissolved in denatured alcohol was then added and the whole stirred on a water bath at 50-60deg C for 2 hours. It was then stripped of volatiles under vaccum to reveal a semi-solid brown residue. At this point I simply flooded the residue with cold dH2O and a white-solid precipitated out of the dark-brown reaction mix; it was isolated by vacuum filtration. The white solid smells like an aldehyde, is insoluble in water, and forms a bisulfite addition product. Yields were not the greatest but I used a huge amount of substrate since all these starting materials are so cheap. However, the question that still remains; in what position has this been formylated?!?
The problem w/refs is that most of my references are from books and I don't have any way to scan them in, of course I can still list them and will upon request. The chloromethylation was completely improvised on my part.. The reaction of 2-nitropropane/NaOH I used for formylation which parallels the sommelet reaction is on rhodium's site at:
https://www.thevespiary.org/rhodium/Rhodium/chemistry/halide.carbonyl.html
, but example two here is more like the procedure I used:
https://www.thevespiary.org/rhodium/Rhodium/chemistry/piperonal.nitronate.html
rhodium; I have done this before; I just didn't like working with alpha-chloromethyl-naphthalene. It was a nasty yellow liquid and so was the 1-naphthaldehyde. Brominating the naphthalene first allowed me to work with a solid product throughout.
Here is another route to the desired aldehyde for NAP which I think I may find preferable to working with grignard's:
Following the beta-sulfonation and hydrolysis to beta-naphthol (see the first posting), the alcohol undergoes ammonlysis to form beta-naphthalamine. This product is then diazotized and reacted with the oxime of formaldehyde (see:
http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=cv5p0139
) to form 2-naphthaldehyde. I am undoubtedly open to any alternative routes to this compound that may be suggested and I appreciate all the interest and input from everyone..